CN1211474C - Deteragent composition containing mixtures of crystallinity-disrupted surfactants - Google Patents

Abstract

A cleaning composition comprising: a) from about 0.1% to about 99.9% by weight of said composition of an alkylaryl sulfonate surfactant system comprising about 10% to about 100% of two or more crystallinity-disrupting alkylaryl sulfonate surfactants of the formula: (B-Ar-D)a(Mq+)b (defined hereinafter); and b) From about 0.00001% to about 99.9%, by weight of the composition, of an adjunct component of a detergent composition, at least one of which is selected from the group consisting of: i) detersive enzymes; ii) organic detergent builders; iii) oxygen bleaches; iv ) bleach activators; v) transition metal bleach catalysts; vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; viii) water-soluble ethoxylated amines with clay soil removal and anti-redeposition properties; ix) polymeric dispersants; x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

Description

Detergent composition containing a mixture of crystallinity-destroying surfactants

field of invention

The present invention relates to detergent compositions comprising an alkylaryl sulfonate surfactant system comprising isomers of crystallinity disrupting, preferably branched, alkylaryl sulfonate surfactants and optionally A mixture of one or more non-crystallinity disrupting alkylaryl sulfonate surfactants. The detergent composition further comprises a detergent additive selected from the group consisting of detersive enzymes, organic detergent builders, oxygen bleaches, bleach activators, transition metal bleach catalysts, oxygen transfer agents and precursors, polymeric soil release agents, clay soil Water-soluble ethoxylated amines, polymeric dispersants, polymeric dye transfer inhibiting agents, alkoxylated polycarboxylates and mixtures thereof for removal and anti-redeposition properties. Cleaning compositions also typically contain additional cleaning composition adjunct ingredients. These cleaning compositions are especially suitable for use in detergent compositions which will be used in laundry processes involving hard water or low water temperature wash conditions.

Background of the invention

Highly branched alkylbenzene sulfonate surfactants such as tetrapropylene-based materials (known as "ABS") have been used in detergents in the past, however, they have been found to be very difficult to biodegrade. There followed a long period of improvement in the process of preparing alkylbenzenesulfonates so that they were as linear ("LAS") as practically possible. The vast majority of the preparation of linear alkylbenzene sulfonate surfactants involves this purpose, and all relevant large-scale industrial alkylbenzene sulfonate preparation methods currently used involve linear alkylbenzene sulfonates. However, the linear alkylbenzene sulfonates are not without limitation, for example they would be more desirable if their properties for hard and/or cold water washing are improved. Thus, they generally do not give good detergency, for example when formulated with non-phosphate builders and/or when used in hard water areas.

Due to the limitations of alkylbenzene sulfonates, consumer wash formulations are often required to include higher levels of co-surfactants, builders and other additives than would be required for the outstanding alkylbenzene sulfonates.

Therefore, there is a strong desire to simplify detergent formulations and provide better performance and better value to consumers. Furthermore, given the very large tonnage of alkylbenzene sulfonate surfactants and detergent formulations used worldwide, even more modern improvements in basic alkylbenzene sulfonate detergent performance would have a significant impact.

To understand the technology of making and utilizing sulfonated alkylaromatic detergents, one will know that it goes through a number of stages, which include (a) the early stage of making highly branched non-biodegradable LAS (ABS); (b) the process of Develop, e.g. HF or AlCl3 catalyzed methods (note that each method gives a different composition, e.g. HF/alkenes give lower 2-phenyl or classical AlCl3/chlorinated paraffins usually give by-products which may be useful for solubility , but is undesirable for biodegradation); (c) the market shift to LAS, where a very high proportion of the alkyl groups are linear; (d) improvements, including the so-called "advanced 2-phenyl" or DETAL method (in fact When the hydrophobe is too linear, it is not actually a "higher" 2-phenyl due to solubility issues); and (e) recent improvements in understanding biodegradation.

The art of alkylbenzene sulfonate detergents in the reference literature is very comprehensive and its teachings relate to and address nearly every aspect of these compositions. For example some techniques teach towards higher 2-phenyl LAS while others teach the exact opposite direction. In addition, there are many false teachings and technical misunderstandings about the mechanism of LAS operation under the conditions of use, especially in terms of hardness tolerance. The abundance of such references derogates the prior art as a whole, making it difficult to select useful techniques from worthless ones without extensive repeated experimentation. To further understand the state of the art, it should be appreciated that not only is there no clarity in identifying unresolved issues with linear LAS, but also that there are many misunderstandings in understanding the biodegradation effects and fundamental mechanisms of LAS operation in the presence of hardness. According to the literature and general practice, relatively insoluble surfactants containing alkali or alkaline earth metal salts (their sodium or calcium salts have relatively high Krafft temperatures) are compatible with alkali or alkaline earth metal salts of relatively high solubility. Ratio (sodium or calcium salts have relatively low Krafft temperature) is less desirable. In the literature, LAS mixtures are considered to precipitate in the presence of free calcium or magnesium hardness. It is also known that the 2- or 3-phenyl or "an" isomer of LAS has a higher Krafft temperature than the 5- or 6-phenyl "endo" isomer. Therefore, one would expect that changing the LAS composition to increase the 2- and 3-phenyl isomer content would reduce hardness tolerance and solubility: not a good thing. On the other hand, it is also known that the 2- and 3-phenyl isomers are more surface active under complexing conditions where both 2- and 3-phenyl and endo-phenyl isomers of equal chain length are soluble substance. Thus, one would expect that changing the LAS composition to increase the 2- and 3-phenyl isomer content would increase wash performance. However, there are still unresolved issues regarding solubility, hardness tolerance, and low-temperature performance.

Background technique

US5026933; US4990718; US4301316; US4301317; US4855527; US4870038; US3238249；US3355484；US3442964；US3492364；US4959491；WO88/07030，9/25/90；US4962256，US5196624；US5196625；EP364012B，2/15/90；US3312745；US3341614；US3442965；US3674885；US444 7664；SU4533651；US4587374；US4996386 US5210060; US5510 306; WO95/17961, 7/6/95; WO95/18084; US5510306; US5087788; For a recent review of the preparation of alkylbenzenesulfonate surfactants, see volume 56 of the "Surfactant Science" series, Marcel Dekker, New York, 1996, including especially Chapter 2, entitled "Alkylarylsulfonate Salts: History, Preparation, Analysis, and Environmental Properties", pp. 39-108, which includes 297 references. All the documents listed therein are listed as references in this paper.

Summary of the invention

We have now surprisingly found that when the alkylaryl sulfonate surfactant system comprises two or more isomers of the crystallinity disrupting alkylaryl sulfonate surfactant, and optionally also contains a or multiple non-crystallinity-destroying alkylarylsulfonate surfactants, with alkylarylsulfonate surfactants that do not include crystallinity-destroying alkylarylsulfonate surfactant isomers A surprising increase in performance compared to the agent system.

The present invention has many advantages over one or more of the above aspects, including, but not limited to: excellent cold water solubility, eg, for cold water washing; outstanding hardness tolerance; and outstanding washability. In addition, the present invention is expected to provide reduced accumulation of old fabric softener residue on laundered fabrics and improved removal of greasy or greasy soils from fabrics. Effects are also expected in non-laundry washing applications, such as dishwashing. The development offers clear and predictable improvements in the ease of preparation of relatively advanced 2-phenylsulfonate compositions, improvements in the ease of manufacture and quality of the resulting detergent formulations, and attractive economic advantages.

The present invention is based on the unexpected discovery that in the intermediate region between the old highly branched non-biodegradable alkylbenzene sulfonates and the new linear types there are certain higher performing and alkylbenzene sulfonates which are more biodegradable than the former.

The neo-alkylbenzene sulfonates are readily prepared by a number of known alkylbenzene sulfonate preparation methods, for example they can be conveniently prepared using certain dealuminated mordenites.

The present invention provides new cleaning compositions comprising:

a) from about 0.1% to about 99.9% by weight of the composition of an alkylaryl sulfonate surfactant system containing from about 10% to about 100% by weight of the surfactant system of either or Various crystallinity disrupting alkylaryl sulfonate surfactants of the formula:

(B-Ar-D)a(Mq+)b

where D is SO ₃ ^- , M is a cation or a mixture of cations, q is the valency of said cation, a and b are numbers selected such that said composition is electrically neutral; Ar is selected from benzene, toluene, and combinations thereof and B contains the sum of at least one primary hydrocarbyl moiety containing 5-20 carbon atoms, preferably 7-16, more preferably 9-15, most preferably 10-14 carbon atoms, and one or more crystallinity-disrupting moieties, wherein the disrupting crystallinity moiety interrupts the hydrocarbyl moiety or a branch of the hydrocarbyl moiety; and wherein the crystallinity disrupting effect of the alkylaryl sulfonate surfactant system is up to its CST as determined by the CST test to the extent that the sodium critical solubility temperature does not exceed about 40° C. and also wherein said alkylaryl sulfonate surfactant system has at least one of the following properties:

Percent biodegradation over tetrapolypropylene benzene sulfonate as determined by the modified SCAS test; and

The weight ratio of non-quaternary to quaternary carbon atoms in B is at least about 5:1 (preferably at least about 10:1; more preferably at least about 100:1); and

b) from about 0.00001% to about 99.9% by weight of the composition of detergent composition adjunct components, at least one of which is selected from the group consisting of: i) detersive enzymes, preferably selected from the group consisting of proteases, amylases, lipases, cellulases , peroxidase and mixtures thereof; ii) organic detergent builders, preferably selected from the group consisting of polycarboxylate compounds, ether hydroxypolycarboxylates, substituted ammonium salts of polyacetic acid and mixtures thereof; iii) oxygen Bleaching agents, preferably selected from hydrogen peroxide, inorganic peroxyhydrates, organic peroxyhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- and di-peroxyacids, and mixtures thereof; iv) bleach activation agent, preferably selected from TAED, NOBS and mixtures thereof; v) transition metal bleach catalyst, preferably manganese-containing bleach catalyst; vi) oxygen transfer agent and precursor; vii) polymeric soil release agent; Water-soluble ethoxylated amines of redeposition properties; ix) polymeric dispersants; x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

Detergent compositions will preferably contain at least about 0.1%, more preferably at least about 0.5%, even more preferably at least about 1%, by weight of the composition, of a surfactant system. The detergent compositions will also preferably contain no more than about 80%, even more preferably no more than about 60%, most preferably no more than about 40%, by weight of the composition, of a surfactant system.

The surfactant system will preferably contain at least about 15%, more preferably at least about 30%, and even more preferably at least about 40%, by weight of the surfactant system, of two or more crystallinity disrupting alkylaryl sulfonates salt surfactants. The surfactant system will also preferably contain no more than about 100%, more preferably no more than about 90%, and even more preferably no more than about 80%, by weight of the surfactant system, of two or more crystallinity-disrupting alkyl groups. Aryl Sulfonate Surfactant.

Accordingly, it is an aspect of the present invention to provide novel cleaning compositions, these and other aspects, features and advantages will be apparent from the following detailed description and appended claims.

All percentages, ratios and proportions herein are by weight of components used to prepare the final composition, unless otherwise specified. All temperatures are in degrees Celsius (°C) unless otherwise indicated. All cited documents are, in relevant part, incorporated herein by reference.

Detailed description of the invention

The present invention relates to novel detergent compositions. Component (a) comprises from about 0.1% to about 99.9% by weight of the composition of an alkylaryl sulfonate surfactant system comprising from about 10% to about 100% by weight of the surfactant system. % of two or more alkylaryl sulfonate surfactants of the formula destroying crystallinity

(B-Ar-D)a(Mq+)b

Wherein D is SO3-, M is a cation or a mixture of cations. M is preferably an alkali metal, alkaline earth metal, ammonium, substituted ammonium or mixtures thereof, more preferably sodium, potassium, magnesium, calcium or mixtures thereof. The valence q of the cation is preferably 1 or 2. The numbers are chosen such that the composition is charge neutral, a and b are preferably 1 or 2 and 1 respectively.

Ar is preferably selected from benzene, toluene and combinations thereof, most preferably benzene.

B contains the sum of at least one primary hydrocarbyl moiety containing 5 to 20 carbon atoms and one or more crystallinity disrupting moieties interrupting or branching the hydrocarbyl moiety. Preferably B includes both odd and even chain length hydrocarbyl moieties, ie preferably B is not limited to being all odd or all even chain length hydrocarbyl moieties. The primary hydrocarbyl moiety of B has 5-20, preferably 7-16 carbon atoms, and there may be 1-3 crystallinity disrupting moieties interrupting said hydrocarbyl moiety or branches of said hydrocarbyl moiety. When the moieties that destroy crystallinity are branched chains, they are preferably C1-C3 alkyl, C1-C3 alkoxy, hydroxyl and mixtures thereof, more preferably C1-C3 alkyl, most preferably C1-C2 alkyl, most preferably Methyl is preferred. These are preferably ethers, sulfones, siloxanes, and mixtures thereof, more preferably ethers, when the crystallinity breaking portion interrupts the hydrocarbyl moiety. Preferred crystallinity disrupting alkylaryl sulfonate surfactants include two or more homologues. The "homologues" contained in B may have a variable number of carbon atoms. "Isomers" which will be described in more detail hereinafter include, inter alia, those compounds whose crystallinity-destroying moieties have different attachment positions to B.

It is also preferred that the crystallinity disrupting alkylaryl sulfonate surfactant comprises at least two "isomers" selected from

i) When Ar is a substituted or unsubstituted benzene, the ortho-, meta- and para-isomers based on the position of attachment of the substituent to Ar. This means that B can be in the ortho-, meta- and para positions of D, B can be in the ortho-, meta- and para positions of substituents other than D on Ar, and D can be in addition to B on Ar Ortho-, meta- and para-positions of substituents or any other possible alternatives;

ii) positional isomers based on the position of attachment of said crystallinity disrupting moiety to said primary hydrocarbyl moiety of B; and

iii) Stereoisomers based on the chiral carbon atom in B.

More preferably the crystallinity disrupting alkylaryl sulphonate surfactant will comprise at least two isomers of type ii), most preferably at least four isomers of type ii).

Preferably at least about 60%, by weight of the surfactant system, of said crystallinity disrupting alkylaryl sulfonate surfactant is in the isomeric form wherein Ar is in the first, second position of said primary hydrocarbyl moiety. B is attached to the second or third carbon atom, more preferably about 70% or more, most preferably about 80% or more.

An optional component of the compositions of the present invention is from about 0% to about 85% by weight of the surfactant system of one or more non-crystallinity disrupting alkylaryl sulfonate surfactants of the formula:

(L-Ar-D)a(Mq+)b

Wherein D, M, q, a, b, Ar are as defined above, L is a straight chain primary hydrocarbyl moiety containing 5-20 carbon atoms, preferably L is a straight chain hydrocarbyl moiety containing 7-16 carbon atoms.

The alkylaryl sulfonate surfactant system has a crystallinity-destroying effect until its sodium critical solubility temperature, as determined by the CST test as defined below, does not exceed about 40°C, preferably does not exceed about 20°C, most preferably does not exceed about 5°C. It is also preferred that it has a calcium critical solubility temperature as determined by the CST test of less than about 80°C, preferably no more than about 40°C, more preferably no more than about 20°C.

The alkylaryl sulfonate surfactant system also has at least one of the following properties:

a) The percent biodegradation, as determined by the modified SCAS test (described below), exceeds tetrapropylene benzene sulfonate; or

b) the weight ratio of non-quaternary to quaternary carbon atoms in B is at least about 5:1, preferably the weight ratio of non-quaternary to quaternary carbon atoms in B is at least about 10:1, more preferably at least about 20:1, and Most preferably at least about 100:1.

More preferably, the percent biodegradation in absolute value is preferably at least about 60%, more preferably at least 70%, still more preferably at least 80% and most preferably at least 90%, as determined in the modified SCAS test.

The detergent compositions of the present invention comprise component (b) which is from about 0.00001% to about 99.9% by weight of the composition of a detergency adjunct material. These, as well as other washing aids, which are optionally used in the present invention are described in detail hereinafter.

destroy crystallinity

The term "disruption of crystallinity" is defined herein to mean that a surfactant in reference contains hydrophobic moieties selected to cause the surfactant to pack into the crystal lattice less efficiently than a reference surfactant, at which The hydrophobe in the reference surfactant is a pure linear hydrocarbon chain of the formula CH3(CH2)n- having a chain length or chain length range comparable to the surfactant.

In general, disruption of crystallinity can result from several modifications at the molecular level of any surfactant. It is worth noting that linear hydrophobes that are themselves "non-crystallinity disrupting", such as

That is, CH3(CH2)11-, can be modified by inserting different moieties in the chain, such as ether moiety, siloxane or sulfone, to form the crystallinity-destroying structure of the present invention, such as:

or

The disrupted crystallinity of the present invention more preferably occurs when one or more branches of B are added to the structure, such as:

or

Note that the present invention has surfactants of the formulas (B-Ar-D)a(Mq+)b and (L-Ar-D)a(Mq+)b, with B representing a crystallinity disrupting hydrophobe and L representing a non-crystallization disrupting Hydrophobic substance. Also in other words, the crystallinity disrupting hydrophobe B contains a primary moiety consisting of (i) all components in B except the crystallinity disrupting fraction and (ii) the crystallinity disrupting fraction.

In a preferred embodiment, B contains (i) moieties containing 7-16 carbon atoms and (ii) crystallinity disrupting moieties selected from (a) branched chains (or "side chains") attached to B which Usually variable, but preferably selected from C1-C3 alkyl, hydroxyl and mixtures thereof, more preferably C1-C3 alkyl, most preferably C1-C2 alkyl, most preferably methyl; (b) Interrupted B structure Moieties selected from ethers, sulfones, siloxanes; and (c) mixtures thereof. Other crystallinity-destroying moieties that are not preferred in the present invention include olefins.

Alkylaryl Sulfonate Surfactant System

The major component of the detergent compositions of the present invention is an alkylaryl sulfonate surfactant system which contains a major crystallinity disrupting component.

The present invention relates to detergent compositions comprising at least two or more of such crystallinity disrupting alkylaryl sulfonate surfactants, and optionally one or more non-crystallinity disrupting alkylaryl sulfonate Surfactant. These two components are described as follows:

(1) Alkylaryl sulfonate surfactants that destroy crystallinity:

The detergent compositions of the present invention comprise an alkylaryl sulfonate surfactant system comprising at least two or more crystallinity disrupting alkylaryl sulfonate surfactants having the formula:

(B-Ar-D)a(Mq+)b

Where D, B, M, q, a, b, Ar are as defined above, possible crystallinity disrupting alkylaryl sulfonate surfactants include:

and

Structures (a)-(o) are merely illustrative of some possible crystallinity disrupting alkylaryl sulfonate surfactants and are not intended to limit the scope of the invention.

It is also preferred that the crystallinity disrupting alkylaryl sulfonate surfactant comprises at least two isomers selected from

i) Ortho-, meta- and para-isomers based on the position of attachment of the substituent to Ar, where Ar is a substituted or unsubstituted benzene. This means that B can be in the ortho-, meta- and para positions of D, B can be in the ortho-, meta- and para positions of substituents other than D on Ar, and D can be in addition to B on Ar Ortho-, meta- and para-positions of substituents or any other possible alternatives;

ii) positional isomers based on the position of attachment of said crystallinity disrupting moiety to said primary hydrocarbyl moiety of B; and

iii) Stereoisomers based on the chiral carbon atom in B.

Examples of two types of (ii) isomers are structures (a) and (c), the difference being that in (a) the methyl group is attached at the 5-position, but in (c) the methyl group is attached at the 7-position.

Examples of two types of (i) isomers are structures (l) and (n), the difference being that in (l) the sulfonate group is in the meta position of the hydrocarbyl moiety, whereas in (n) the sulfonate is in ortho to the hydrocarbyl moiety.

Examples of two type (iii) isomers are structures (c) and (d), the difference being that these isomers are stereoisomers and the chiral carbon atom is the 7th carbon atom in the hydrocarbyl moiety.

(2) Alkylaryl sulfonate surfactants that do not destroy crystallinity

The detergent compositions of the present invention also optionally contain an alkylaryl sulfonate surfactant system comprising one or more non-crystallinity disrupting alkylaryl sulfonate surfactants of the formula:

(L-Ar-D)a(Mq+)b

wherein D, M, L, q, a, b, Ar are as defined above. Possible non-crystallinity disrupting alkylaryl sulfonate surfactants include standard linear alkylbenzene sulfonates such as commercially available materials such as the so-called higher 2-phenyl linear alkylbenzene sulfonates salt, better known as DETAL or conventional LAS from Huntsman or Vista. These linear alkylaryl sulfonates may be added with crystallinity disrupting alkylaryl sulfonate surfactants to provide the alkylaryl sulfonate surfactant system for use in the cleaning compositions of the present invention. In addition, the non-crystallinity-destroying alkylaryl sulfonate surfactant and the crystallinity-destroying alkylaryl sulfonate surfactant can be used with the same Reaction preparation. The ratio of non-crystallinity-destroying alkylaryl sulfonate to crystallinity-destroying alkylarylsulfonate depends on the catalyst used. No matter which catalyst is used, the surfactant system must have a sodium critical solubility temperature of not more than about 40° C., and a percent biodegradation measured by the modified SCAS test in excess of tetrapropylene benzenesulfonate, preferably greater than 60%, more preferably Preferably greater than 80%, or a weight ratio of non-quaternary to quaternary carbon atoms in B of at least about 5:1.

Example 1

Crystallinity-disrupting surfactant systems prepared from skeletally isomerized linear olefins

Step (a): At least partially reduce the linearity of the olefin (by prefabricating the product suitable for washing Skeletal isomerization of olefins with fouling chain lengths)

1-decene, 1-undecene, 1-dodecene, and 1-tridecene (obtained, for example, from Chevron) in a weight ratio of 1:2:2:1 at 220° C. and any suitable LHSV, eg 1.0 over Pt-SAPO catalyst. The catalyst is prepared by the method in Example 1 of US5082956. See WO 95/21225 for example Example 1 and description thereof. The product is skeletally isomerized to lightly branched olefins having a chain length range suitable for making alkylbenzene sulfonate surfactants for incorporation into consumer cleaning compositions. The temperature in this step may more typically be from about 200°C to about 400°C, preferably from about 230°C to about 320°C. The pressure is generally from about 15 psig to about 2000 psig, preferably from about 15 psig to about 1000 psig, more preferably from about 15 psig to about 600 psig. Hydrogen is a useful pressurized gas. The space velocity (LHSV or WHSV) is suitably from about 0.05 to about 20. Low pressure and low spatiotemporal velocity provide improved selectivity, more isomerization and less cracking. Any volatiles boiling up to 40°C/10 mmHg were removed by distillation.

Step (b): Alkylation of the product of step (a) with an aromatic hydrocarbon

Into a glass autoclave liner was charged one molar equivalent of the lightly branched olefin mixture prepared in step (a), 20 molar equivalents of benzene and 20 wt. ^TM FM-8/25H). The glass liner was sealed in a stainless steel swinging autoclave which was purged twice with 250 psig nitrogen and then filled to 1000 psig nitrogen. With mixing, the mixture was heated to 170-190°C for 14-15 hours, after which it was cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst, and the product is obtained as a clear, nearly colorless liquid by distilling off unreacted starting material and/or impurities (eg benzene, olefins, paraffins, traces, useful materials recycled if desired). The product can then be formed into the desired crystallinity-destroying surfactant system, which can optionally be transported to a remote manufacturing facility where additional sulfonation steps can be performed and incorporated into consumer cleaning compositions.

Step (c): Sulfonation of the product of step (b)

The product of step (b) is sulfonated with an equivalent of chlorosulfonic acid using dichloromethane as a solvent, and the dichloromethane is distilled off.

Step (d): Neutralization of the product of step (c)

The product of step (c) is neutralized with sodium methoxide in methanol and evaporation of the methanol yields a crystallinity-destroying surfactant system.

Example 2

Crystallinity-disrupting surfactant systems prepared from skeletally isomerized linear olefins

The method of Example 1 was repeated except that sulfur trioxide (without dichloromethane solvent) was used as the sulfonating agent in the sulfonation step (c). Details of sulfonation with suitable air/sulfur trioxide mixtures are given in US3427342 to Chemithon. In addition, step (d) uses sodium hydroxide instead of sodium methoxide for neutralization.

Example 3

Crystallinity-disrupting surfactant systems prepared from skeletally isomerized linear olefins

Step (a): At least partially reducing the linearity of the alkene

A mixture of lightly branched olefins was prepared by passing a mixture of C11, C12 and C13 monoolefins in a weight ratio of 1:3:1 over a H-ferrierite catalyst at 430°C. The method and catalyst of US5510306 can be used for this step. Any volatiles boiling up to 40°C/10 mmHg were removed by distillation.

Step (b): Alkylation of the product of step (a) with an aromatic hydrocarbon

Into a glass autoclave liner was charged one molar equivalent of the lightly branched olefin mixture prepared in step (a), 20 molar equivalents of benzene and 20% by weight of the shape-selective zeolite catalyst (acidic mordenite catalyst Zeocat ^TM FM-8/25H). The glass liner is sealed in a stainless steel swing autoclave. The autoclave was purged twice with 250 psig nitrogen and then filled to 1000 psig nitrogen. With mixing, the mixture was heated to 170-190° C. overnight for 14-15 hours, after which it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst. The benzo is distilled off and recycled, and volatile impurities are removed. A clear, colorless or nearly colorless liquid product is obtained.

Step (c): Sulfonation of the product of step (b)

The product of step (b) is sulfonated with an equivalent of chlorosulfonic acid using dichloromethane as a solvent, and the dichloromethane is distilled off.

Step (d): Neutralization of the product of step (c) The product of step (c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to obtain a crystallinity-destroying surfactant system, sodium salt mixture.

Example 4

Crystallinity-destroying surfactant systems prepared by skeletal isomerization of paraffins

step (ai)

The 1:3:1 (weight) mixture of n-undecane, n-dodecane, n-tridecane is on Pt-SAPO-11 at about 300-340 ℃, under 1000 psig hydrogen pressure, with the weight of 2-3 Hourly space velocity and 30 moles of H2/mole of hydrocarbon isomerizes at over 90% conversion. A more detailed description of this isomerization is given by S.J. Miller in Microporous Materials, Vol. 2 (1994), 439-449. In other embodiments, the linear starting paraffin mixture can be the same as those used for conventional LAB preparation. Any volatiles boiling up to 40°C/10 mmHg were removed by distillation.

step (aii)

The paraffins of step (ai) can be dehydrogenated by conventional methods. See eg US5012021, 4/30/91 or US3562797, 2/9/71. Suitable dehydrogenation catalysts are any of the catalysts disclosed in US Pat. For the examples used in the present invention, the dehydrogenation was carried out according to US3562797 and the catalyst was zeolite A. The dehydrogenation takes place in the vapor phase in the presence of oxygen (paraffin:molecular oxygen 1:1 molar). The temperature was 450°C to 550°C and the ratio of grams of catalyst to moles of total feed per hour was 3.9.

Step (b): Alkylation of the product of step (a) with an aromatic hydrocarbon

One molar equivalent of the mixture of step (a), 5 molar equivalents of benzene and 20 wt% shape selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ FM-8/25H) based on the olefin mixture were added to a glass autoclave liner. The glass liner is sealed in a stainless steel swing autoclave. The autoclave was purged twice with 250 psig nitrogen and then filled to 1000 psig nitrogen. With mixing, the mixture was heated to 170-190° C. overnight for 14-15 hours, after which it was cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst, and the benzene and any unreacted paraffin are distilled off and recycled to yield a clear, colorless or nearly colorless liquid product.

Step (c): Sulfonation of the product of step (b)

The product of step (b) is sulfonated with sulfur trioxide/air without solvent, see US3427342. The molar ratio of sulfur trioxide to alkylbenzene is from about 1.05:1 to about 1.15:1. The reactant stream is cooled and separated from excess sulfur trioxide.

Step (d): Neutralization of the product of step (c)

Neutralization of the product of step (c) with a slight excess of sodium hydroxide results in a crystallinity-destroying surfactant system.

Example 5

     Prepared by the Grignard reaction through a mixture of special tertiary alcohols

       Surfactant systems that disrupt crystallinity

A mixture of 5-methyl-5-undecanol, 6-methyl-6-dodecanol and 7-methyl-7-tridecanol was prepared via the following Grignard reaction. A mixture of 28 g 2-hexanone, 28 g 2-heptanone, 14 g 2-octanone and 100 g diethyl ether was added to the addition funnel. The ketone mixture was then added dropwise over 1.75 hours to a nitrogen blanketed stirred three necked round bottom flask equipped with a reflux condenser and containing 350 ml of 2.0 M hexylmagnesium bromide in ether and an additional 100 ml of ether. After the addition was complete, the reaction mixture was stirred for an additional 1 hour at 20°C. The reaction mixture was then added to a 600 g mixture of ice and water with stirring. To this mixture was added 228.6 g of a 30% sulfuric acid solution. Add the resulting two liquid phases to a separatory funnel. The aqueous layer was drained and the remaining ether layer was washed twice with 600 mL of water. The ether layer was then evaporated in vacuo to give 115.45 g of the desired alcohol mixture. A 100 g sample of the light yellow alcohol mixture was charged into a glass autoclave liner along with 300 ml benzene and 20 g shape selective zeolite catalyst (acid mordenite catalyst Zeocat ^™ FM-8/25H). The glass liner was sealed in a stainless steel swinging autoclave which was purged twice with 250 psig nitrogen and then filled to 1000 psig nitrogen. With mixing, the mixture was heated to 170° C. overnight for 14-15 hours, after which it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst, concentrated by distilling off the benzene, which was dried and recycled. A transparent, colorless or nearly colorless mixture of slightly branched olefins is obtained.

50 g of the above lightly branched olefin mixture obtained by dehydrating Grignard alcohol mixture were charged into a glass autoclave lining together with 150 ml of benzene and 10 g of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat ^™ FM-8/25H). The glass liner was sealed in a stainless steel swinging autoclave which was purged twice with 250 psig nitrogen and then filled to 1000 psig nitrogen. With mixing, the mixture was heated to 195°C overnight for 14-15 hours, after which it was cooled and removed from the autoclave. The reaction mixture was filtered to remove the catalyst, concentrated by distilling off the benzene, which was dried and recycled. A clear, colorless or nearly colorless liquid product is obtained. The product was distilled under vacuum (1-5 mmHg) and the 95°C-135°C fraction remained.

The remaining fraction, a clear colorless or nearly colorless liquid product, is subsequently sulfonated with a molar equivalent of SO3, the resulting product is neutralized with sodium methoxide in methanol, and evaporation of the methanol yields a crystallinity-destroying surfactant system.

Critical Solubility Temperature Test or CST Test

The critical solubility temperature test is to determine the critical solubility temperature of the surfactant system. Briefly, the critical solubility temperature is the temperature at which a surfactant system is measured at which there is a sudden and pronounced increase in solubility. With the current trend towards lower and lower wash temperatures, this temperature is becoming more and more important. We have surprisingly found that the amount and type of crystallinity destroying alkylarylsulfonate surfactants present in the alkylarylsulfonate surfactant system can reduce the The critical solubility temperature of a surfactant system.

The critical solubility temperature was determined by the following method:

All glassware used was washed and thoroughly dried, and all temperatures were measured with a calibrated mercury thermometer. The sample weights employed are based on the dry form of the solid surfactant or surfactant mixture.

A) Sodium Critical Solubility Temperature - 99 g of deionized water was added to a clean dry beaker with a magnetic stirrer. The beaker was then placed in an ice-water bath until the deionized water cooled to 0 °C. A 1.0 g sample of the solid sodium salt of the surfactant or mixture of surfactants for which the sodium critical solubility temperature is to be measured is then added. The resulting heterogeneous solution was stirred for 1 hour. If the surfactant sample dissolves within 1 hour to give a clear homogeneous solution without any heating, the sodium critical solubility temperature is recorded as ≤0°C. If the surfactant sample does not dissolve within 1 hour to give a clear homogeneous solution, slowly heat the heterogeneous solution at a rate of 0.1°C per minute with stirring. Record the temperature at which the surfactant sample dissolves to obtain a transparent homogeneous solution as the critical solubility temperature of sodium.

B) Calcium Critical Solubility Temperature - 99 g of deionized water was added to a clean dry beaker with a magnetic stirrer. The beaker was then placed in an ice-water bath until the deionized water cooled to 0 °C. A 1.0 g sample of the solid calcium salt of the surfactant or mixture of surfactants for which the critical solubility temperature of calcium is to be measured is then added. The resulting heterogeneous solution was stirred for 1 hour. If the surfactant sample dissolves within 1 hour to give a clear homogeneous solution without any heating, the critical calcium solubility temperature is recorded as ≤0°C. If the surfactant sample does not dissolve within 1 hour to give a clear homogeneous solution, slowly heat the heterogeneous solution at a rate of 0.1°C per minute with stirring. Record the temperature at which the surfactant sample dissolves to obtain a transparent homogeneous solution as the critical solubility temperature of calcium.

The sodium salt of the surfactant mixture of the present invention is the most common form in which the surfactant mixture is used. Conversion to calcium salts by simple metathesis, for example in dilute solution or by means of suitable organic solvents, is known.

Modified SCAS test

This method was adapted from the Soap and Detergent Society Semi-Continuous Activated Sludge Test (SCAS) method to assess the primary biodegradation of alkylbenzene sulfonates. The method involves exposing chemicals to relatively high concentrations of microorganisms over an extended period of time (perhaps several months). During this time the viability of the microorganisms was maintained by the daily addition of settled sewage feed. This modified test is also the standard OECD test for intrinsic biodegradability or 302A, which was adopted by the OECD on May 12, 1981. A detailed description of the "unmodified" SCAS test can be found in "Methods and Criteria for Determining the Biodegradability of Alkylbenzene Sulfonates and Linear Alkyl Sulfonates", Journal of the American Oil Chemists' Society, Found in Vol. 42, p. 986 (1965).

It is most useful as a test of intrinsic biodegradability when a surfactant or surfactant system is tested to show a high potential for biodegradation.

The aeration device used was the same as disclosed in the "unmodified" SCAS trial, namely an 83 mm (3 1/4 inch) I.D. (inside diameter) Plexiglas tube with a taper of 13 mm (1/4 inch) from the hemisphere perpendicular to the bottom. 2 inches) taper at 30° to the lower end, 25.4mm (1 inch) above the junction of the vertical and tapered walls to set the bottom of the 25.4mm (1 inch) diameter port for insertion of the air delivery tube. The total length of the aeration chamber shall be at least 600mm (24 inches). An optional drain can be provided at a height of 500ml to facilitate sampling. The device remains open to atmosphere. Air is delivered to the aeration unit by a small laboratory-scale air compressor. Air is filtered through glass wool or any other suitable medium to remove contaminants, oil, etc. The air is also presaturated with water to reduce evaporation losses from the unit. The air is provided at a rate of 500 ml/min (1ft3/hour), and the air is provided by a 8mmO.D. (outer diameter), 2mmI.D. capillary, and the end of the capillary is located 7mm (1/4 inch) from the bottom of the aeration chamber. place.

Modified SCAS Test - Aerators are cleaned and fixed in suitable brackets. The procedure is carried out at 25 °C + 3 °C to prepare a stock solution of the test surfactant or surfactant system: since organic carbon typically yields 20 mg/l carbon at the beginning of each biodegradation cycle if no biodegradation occurs Surfactant or surfactant system concentration, usually required concentration is 400mg/l.

A sample of the mixed liquor was obtained from an activated sludge plant that mainly treats domestic sewage. Fill each aeration device with 150ml of mixed solution and start aeration. After 23 hours, the aeration was stopped and the sludge was allowed to settle for 45 minutes. Remove 100ml supernatant. Samples of settled domestic sewage were obtained immediately before use, and 100 ml were added to the sludge remaining in each aerator. The aeration was restarted, no test substance was added at this stage, and the device was fed only domestic sewage every day until a clear supernatant was obtained when settling. This usually takes up to two weeks, at which point the dissolved organic carbon in the supernatant should be less than 12 mg/l at the end of each aeration cycle.

At the end of this period, the individual settled sludges were mixed and 50 ml of the resulting composite sludge was added to each unit.

100ml of settled sewage was added to the aeration unit, which will serve as a control unit. Add 95 ml of settled sewage and 5 ml of the appropriate test surfactant or surfactant system stock solution (400 mg/l) to the aeration unit, which will serve as a control unit. Aeration was restarted and continued for 23 hours. The sludge was then allowed to settle for 45 minutes and the supernatant was removed and analyzed for dissolved organic carbon content. Carbon content (D.O.C.) was analyzed with SHIMADZU, model TOC-5000 TOC analyzer. The addition and removal process was repeated daily throughout the test, and the walls of the apparatus needed to be cleaned prior to settling to avoid accumulation of solids above the liquid level. Use separate spatulas or brushes for each device to avoid cross-contamination.

Ideally, the dissolved organic carbon in the supernatant should be measured daily, although less frequent analyzes are permitted. Solutions were filtered through washed 0.45 micron membrane filters and centrifuged prior to analysis. The temperature of the sample must not exceed 40°C during centrifugation.

The dissolved organic carbon results in the supernatants in the test and control aerators were plotted against time. Due to biodegradation, the levels in the test aerators will be close to those in the control aerators. Once the difference between the two levels remains constant over three consecutive measurements, the results of the next three measurements are recorded and the percent biodegradation of the test surfactant or surfactant system is calculated from the following formula:

in

OT = concentration of test surfactant or surfactant system at the beginning of the aeration cycle as organic carbon added to settled sewage

Ol = concentration of dissolved organic carbon measured in the supernatant of the test aerator at the end of the aeration cycle.

Oc = concentration of dissolved organic carbon measured in the supernatant of the control aerator.

The degree of biodegradation is thus the percent removal of organic carbon.

For tetrapolypropylene benzene sulfonate ("TPBS", see "Surfactant Science Series", vol. 56, Marcel Dekker, N.Y., 1996, p. 43), this modified test provides the following data (e.g. for intrinsic biodegradation Standard OECD test for capability or reported on page 7 of 302A):

Test surfactant or form OT(mg/l) Ol-Oc(mg/l) % biodegradation

surfactant system

TPBS 17.3 8.4 51.4

detergent composition

The detergent compositions of the present invention comprise a variety of consumer laundry product compositions including powders, liquids, granules, gels, pastes, tablets, sachets, bars, types provided in dual compartment containers, sprays or foam detergents and other homogeneous or heterogeneous consumer wash product forms. They can be used or applied by hand and/or in single or freely variable doses or by automatic dispensing devices, or can be used in appliances, such as washing machines or dishwashing machines, or can be used for public cleaning, including for example personal cleaning in public facilities , for bottle washing, for surgical instrument washing or for washing electronic components. They can have a wide range of pH, such as about 2 to about 12 or higher, they can have a wide range of alkaline reserves, which can include very high alkaline reserves when used, such as drain-connected, where every 100 grams of Several tens of grams of NaOH equivalent can be present in the formulation, ranging from 1-10 grams of NaOH equivalent and the mildly alkaline or low alkaline range of liquid hand sanitizers, down to the acid side, such as acidic hard surface cleaners. Includes high suds and low suds detergent types.

Consumer Product Detergent Compositions in "Surfactant Science Series", Marcel Dekker, New York, vol. 1-67 and subsequent volumes. Liquid compositions are described in detail in Volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9, incorporated herein by reference. More classical formulations, especially of the granular type, are described in "Preparation of Detergents Including Zeolite Builders and Other New Materials", Ed. M. Sittig, Noyes Data Corporation, 1979, incorporated herein by reference. See also Kirk Othmer's Encyclopedia of Chemical Technology.

Consumer product cleaning compositions of the present invention include, but are not limited to:

Light Duty Liquid Detergents (LDL): These compositions include magnesium ions with improved surface activity (see e.g. WO97/00930A, GB2292562A, US5376310, US5269974, US5230823, US4923635, US4681704, US4316824, US4133779) and/or organic diamines and /or various foam stabilizers and/or foam boosters, such as amine oxides (see for example US4133779) and/or skin feel improvers of surfactants, emollients and/or enzyme types, including proteases and/or antibacterial agents A more comprehensive patent is given in Surfactant Science Series Vol. 67, pp. 240-248.

Heavy Duty Liquid Detergents (HDL): These compositions include so-called "structured" or heterogeneous (see for example US4452717, US4526709, US4530780, US4618446, US4793943, US4659497, US4871467, US4891147, US5006273, US50215195, US5147576) 1 and "unstructured" or isotropic liquid types, which may generally be aqueous or non-aqueous (see e.g. US4655954、US4661280、EP225654、US4690771、US4744916、US4753750、US4950424、US5004556、US5102574、WO94/23009；和可含有漂白剂(参见例如US4470919、US5250212、EP564250、US5264143、US5275753、US5288746、WO94/11483、EP598170、EP598973、 EP619368、US5431848、US5445756)和/或酶(参见例如US3944470、US4111855、US4261868、US4287082、US4305837、US4404115、US4462922、US45295225、US4537706、US4537707、US4670179、US4842758、US4900475、US4908150、US5082585、US5156773、WO92/19709、EP583534 , EP583535, EP583536, WO94/04542, US5269960, EP633311, US5422030, US5431842, US5442100) or without bleach and/or enzymes. Other patents covering heavy duty liquid detergents are in Surfactant Science Series, Vol. 67, No. 309 - Tabulated or listed on page 324.

Heavy Duty Granular Detergents (HDG): These compositions include so-called "compact" or agglomerated or otherwise non-spray-dried, and so-called "loose" or spray-dried types. They include phosphate and non-phosphate types. The detergent may comprise the more commonly used anionic surfactant-based type or may be of the so-called "high nonionic" type, where typically the nonionic surfactant is held in an adsorbent such as a zeolite or other porous inorganic salt or surface. HDG的制备在例如EP753571A、WO96/38531A、US5576285、US5573697、WO96/34082A、US5569645、EP739977A、US5565422、EP737739A、WO96/27655A、US5554587、WO96/25482A、WO96/23048A、WO96/22352A、EP709449A、WO96/09370A , US5496487, US5489392 and EP694608A disclosed.

"Softeners" (STW): These compositions include various granules or liquids (see for example EP753569A, US4140641, US4639321, US4751008, EP315126, US4844821, US4844824, US4873001, US4911852, US5017296, EP422787) of the softening type during the washing process. The product, typically may contain organic (eg quaternized) or inorganic (eg clay) softeners.

Hard Surface Cleaners (HSC): These compositions include all-purpose cleaners, such as cream cleaners and liquid all-purpose cleaners, spray all-purpose cleaners, including glass and tile cleaners, and bleach spray cleaners; and include bathroom cleaners, including Anti-mold, containing bleach, antibacterial, acidic, neutral and alkaline types. See eg EP743280A, EP743279A. Acid cleaners include those in WO96/34938A.

Bar soaps (BS & HW): these compositions include personal washing bars as well as so-called laundry bars (see eg WO96/35772A); including synthetic detergent and soap based types and types containing softeners (see US5500137 or WO96/01889A); The compositions may include products manufactured by conventional soapmaking techniques, such as plodding, and/or less conventional techniques, such as casting, adsorption of surfactants in porous carriers, and the like. Other bar soaps are also included (see eg BR9502668, WO96/04361A, WO96/04360A, US5540852). Other hand wash detergents include those described in GB2292155A and WO96/01306A.

Shampoos and conditioners (S&C): (see eg WO92/37594A, WO96/17917A, WO96/17590A, WO96/17591A). The compositions generally include single shampoos and so-called "two-in-one" or conditioner-containing types.

Liquid Soaps (LS): These compositions include so-called "antibacterial" and conventional types, as well as products with or without skin conditioning agents, including those suitable for use in pump dispensers and other devices such as wall-hung soaps for use in public places The type of device.

Fabric softeners (FS): These compositions include conventional liquid and liquid concentrate types (see for example EP754749A, WO96/21715A, US5531910, EP705900A, US5500138) as well as dryer-added or soil-borne types (see for example US5562847, US5559088, EP704522A). Other fabric softeners include solids (see eg US5505866).

Also included are special purpose cleaners (SPC), including household dry cleaning systems (see eg WO96/30583A, WO96/30472A, WO96/30471A, US5547476, WO96/37652A); bleach pretreatment products for laundry (see EP751210A); Fabric care pre-treatment products (see for example EP752469A); liquid delicate fabric detergent types, especially high sudsing types; rinse aids for dishwashing; liquid bleaches including chlorine and oxygen bleaching types; and disinfectants, rinses Mouth washes, denture cleaners (see for example WO96/19563A, WO96/19562A), car or carpet cleaners or shampoos (see for example EP751213A, WO96/15308A), hair rinses, shower gels, foam baths and personal care cleaners ( See for example WO96/37595A, WO96/37592A, WO96/37591A, WO96/37589A, WO96/37588A, GB2297975A, GB2297762A, GB2297761A, WO96/17916A, WO96/12468A) and metal cleaners; and detergent builders such as bleach additives and "Stain stick" or other pre-treatment types, including special foam types of cleaners (see eg EP753560A, EP753559A, EP753558A, EP753557A, EP753556A) and anti-sunfading treatments (see WO96/03486A, WO96/03481A, WO96/03369A) .

Detergents containing long-lasting fragrances (see eg US5500154, WO96/02490A) are gaining popularity.

Laundry or washing aid substances and methods

The detergent compositions of the present invention contain from about 0.00001% to about 99.9% by weight of at least one detergency adjunct material selected from the group consisting of: i) detersive enzymes, preferably proteases, amylases, lipases, cellulases, Oxidases and mixtures thereof; ii) organic detergent builders, preferably selected from the group consisting of polycarboxylate compounds, ether hydroxypolycarboxylates, substituted ammonium salts of polyacetic acids and mixtures thereof; iii) oxygen bleaches , preferably selected from hydrogen peroxide, inorganic peroxyhydrates, organic peroxyhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- and diperoxyacids, and mixtures thereof; iv) bleach activators, Preferably selected from TAED, NOBS and mixtures thereof; v) transition metal bleach catalysts, preferably manganese-containing bleach catalysts; vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; viii) have clay soil removal and anti-redeposition ix) polymeric dispersants; x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

In general a laundry or cleaning adjunct ingredient is any material required to convert a composition containing only a minimum of essential ingredients into a composition for laundry or cleaning use. In a preferred embodiment, laundry or cleaning adjunct components are readily apparent to those skilled in the art as being absolutely specific to laundry or cleaning products, especially those intended for direct consumer use in a domestic environment. confirm.

The precise nature of these additional ingredients and the levels thereof will depend upon the physical form of the composition and the nature of the laundering operation in which it is employed.

If used with bleach, the adjunct components should preferably have good stability. Due to regulatory requirements, certain preferred detergent compositions of the present invention should be free of boron and/or phosphate. Adjunct components are present at levels of from about 0.00001% to about 99.9%, typically from about 70% to about 95%, by weight of the composition. The use level of the total composition can vary widely depending on the intended application, for example from a few ppm in solution to the so-called "direct application" of neat cleaning composition on the surface being cleaned.

Typically adjunct components include builders, surfactants, enzymes, polymers, bleaches, bleach activators, catalytic Substance etc. Other adjunct components of the present invention may include different active ingredients or special substances, such as dispersant polymers (obtained, for example, from BASFCorp. or Rohm & Haas), stains, silver care agents, rust inhibitors and and/or preservatives, dyes, fillers, bactericides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizers, pro-fragrances, fragrances, solubilizers, carriers, processing aids, pigments, and for liquid formulations solvent.

Quite typically laundry or washing compositions of the present invention such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic and soap based laundry soaps, fabric softeners and fabric treatment liquids, solids and treatment articles of all kinds will Several adjunct components are required, although some simply formulated products, such as bleach additives, require only eg oxygen bleach and the surfactants described herein. A full description of suitable laundry or cleaning adjunct substances can be found in US Provisional Patent Application 60/053319, assigned to Procter & Gamble, filed July 21, 1997.

Detersive Surfactant - The compositions of the present invention desirably include a detersive surfactant. Detersive Surfactants US3929678, Laughlin et al., Dec. 30, 1975 and US4259217, Murphy, Mar. 31, 1981, Series "Surfactant Science," MarcelDekker, Inc., New York and Basel; at "Handbook of Surfactants", MR Porter, Chapman and Hall, 2nd ed., 1994; in "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987; and in Assignment to Procter & Gamble and other detergent and consumer product manufacturers' patents relating to detergents.

Thus, the detersive surfactants of the present invention include surfactants of the anionic, nonionic, zwitterionic or amphoteric types known to be used as detergents for fabric laundering, but do not include completely non-foaming or completely insoluble surfactants. (although they can be used as optional auxiliary components). Examples of the types of surfactants considered optional for use herein are relatively less commonly used than detersive surfactants, but include for example common fabric softener materials such as dioctadecyl dimethyl chloride ammonium chloride.

More specifically, detersive surfactants useful herein, typically at levels of from about 1% to about 55% by weight, suitably include: (1) conventional alkylbenzene sulfonates; (2) olefin sulfonates , including α-olefin sulfonates and sulfonates derived from fatty acids and fatty esters; (3) Alkyl or alkenyl succinate sulfonates, including diester and half-ester types, and sulfosuccinamic acid salts and other sulfonate/carboxylate surfactant types such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; (4) paraffinic or paraffinic sulfonate- and alkyl or alkene (5) alkylnaphthalene sulfonates; (6) alkylisethionates and alkoxypropanesulfonic acids salts, and fatty isethionates, fatty esters of ethoxylated isethionic acid and other ester sulfonates, such as 3-hydroxypropanesulfonate or esters of the AVANEL S type; (7) especially for hydrophobic benzene, cumene, toluene, xylene and naphthalene sulfonates; (8) alkyl ether sulfonates; (9) alkylamide sulfonates; (10) α-sulfo fatty acid salts or esters and (11) Alkyl glyceryl sulfonates; (12) Lignosulfonates; (13) Petroleum sulfonates, sometimes called heavy alkylate sulfonates; (14) Diphenyloxydisulfonates; (15) Linear or branched alkyl or alkenyl sulfates; (16) Alkyl or alkylphenol alkoxylate sulfates and corresponding polyalkoxylates , sometimes called alkyl ether sulfates, and alkenyl alkoxy sulfates or alkenyl polyalkoxy sulfates; (17) alkylamide sulfates or alkenyl amide sulfates, including sulfated alkanolamides and their alkoxylates and polyalkoxylates; (18) sulfated oils, sulfated alkyl glycerides, sulfated alkyl polyglycosides or sulfated sugar derived surfactants; (19) alkyl alkanes Oxycarboxylates and alkyl polyalkoxycarboxylates, including galacturonates; (20) Alkyl and alkenyl ester carboxylates; (21) Alkyl or alkenyl carboxylic acids Salts, especially conventional soaps and α,ω-dicarboxylates, also including alkyl and alkenyl succinates; (22) alkyl or alkenyl amide alkoxy- and polyalkoxy-carboxylates; (23) Alkyl and alkenyl amido carboxylate surfactant types, including sarcosinates, taurates, glycinates, aminopropionates, and iminopropionates; (24) amide soaps, sometimes (25) Alkyl polyaminocarboxylates; (26) Phosphorus-based surfactants, including alkyl or alkenyl phosphate esters, alkyl ether phosphates, including their alkoxylated derivatives phosphatidates, alkyl phosphonates, alkyl di(polyoxyalkylene alkanol) phosphates, amphoteric phosphates such as lecithin; and phosphates/carboxylates, phosphates/sulfates and phosphoric acid Salt/sulfonate types; (27) Pluronic- and Tetronic-type nonionic surfactants; (28) so-called EO/PO block polymers, including di-block and tri-block EPE and PEP types; ( 29) Polyglycol esters of fatty acids; (30) Blocked and unblocked alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, including fatty alcohol polyglycol ethers; (31) Fatty alcohols, especially when used as viscosity adjusting surfactants or present as unreacted components of other surfactants; (32) N-alkyl polyhydroxy fatty acid amides, especially alkyl N-alkyl glucamides; ( 33) Nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkyl polyglycosides, and sucrose fatty acid esters; (34) Ethylene glycol-, propylene glycol-, glycerol- and polyglycerol- Esters and their alkoxylates, especially glyceryl ethers and fatty acids/mono- and di-glycerides; (35) Aldobiose amide surfactants; (36) Alkyl succinimide nonionic surfactant types (37) acetylenic alcohol surfactants, such as SURFYNOLS; (38) alkanolamide surfactants and their alkoxylated derivatives, including fatty acid alkanolamides and fatty acid alkanolamide polyglycol ethers; (39) Alkyl pyrrolidones; (40) Alkyl amine oxides, including alkoxylated or polyalkoxylated amine oxides and amine oxides derived from sugars; (41) Alkyl phosphine oxides; (42) Sulfoxide surfaces Active agents; (43) amphoteric sulfonates, especially sulfobetaines; (44) amphoteric substances of the betaine type, including types derived from aminocarboxylates; (45) amphoteric sulfates, such as alkylammonium polyethylene glycol (46) Alkylamines and amine salts derived from fats and petroleum; (47) Alkylimidazolines; (48) Alkylamidoamines and their alkoxylates and polyalkoxylate derivatives and (49) conventional cationic surfactants, including water-soluble alkyltrimethylammonium salts. Additionally, less commonly used surfactant types are included such as: (50) alkylamidoamine oxides, carboxylates, and quaternized salts; (51) sugar-derived surfaces that mimic the more conventional non-sugar types mentioned above Active agents; (52) Fluorinated surfactants; (53) Biosurfactants; (54) Silicone surfactants; (55) Dual-structure surfactants other than the above-mentioned diphenyloxydisulfonates , including substances derived from glucose; (56) polymeric surfactants, including amphoteric polycarboxyglycinate; and (57) surfactants with hydrophilic groups at both ends.

With regard to the conventional alkylbenzene sulfonates described above, especially for the substantially straight chain types, including those prepared by alkylation with AlCl3 or HF, suitable chain lengths are from about C10 to about C14. The linear alkylbenzene sulfonate surfactant may be present in the compositions of the present invention as a result of separate preparation and incorporation, or as a precursor to one or more surfactants that primarily disrupt crystallinity The consequences that exist are present in the compositions of the present invention. The ratio of linear and crystallinity-disrupting alkylbenzene sulfonates of the present invention can be from 100:1 to 1:100, more typically at least about 0.1 parts by weight when alkylbenzene sulfonates are used, preferably at least About 0.25 parts by weight is the crystallinity disrupting surfactant of the present invention.

In any of the above detersive surfactants, the hydrophobe chain length will generally be C8-C20, preferably a chain length of C8-C18, especially when the wash is performed in cold water. The choice of chain length and degree of alkoxylation for customary use is taught in standard texts. When the detersive surfactant is a salt, any compatible cation may be present, including H (i.e., the acid or partial acid form of a latent acidic surfactant may be used), sodium, potassium, magnesium, ammonium or alkanolammonium or combination of cations. Mixtures of detersive surfactants having different charges are generally preferred, especially anionic/cationic, anionic/nonionic, anionic/nonionic/cationic, anionic/nonionic/ampphoteric, nonionic/cationic and nonionic/ampphoteric mixtures. Furthermore, any single detersive surfactant can be replaced by other surfactants having different chain lengths, degrees of unsaturation or branching, degrees of alkoxylation (degree of ethoxylation), substituents such as ether oxygen atoms in hydrophobes Intercalation, or any combination thereof, of similar detersive surfactant mixture substitutions generally have the desired results for cold water washes.

Preferred among the above detersive surfactants are: C9-C20 linear alkylbenzene sulfonic acids, sodium and ammonium, especially linear secondary alkyl C10-C15 sodium benzenesulfonates (1); olefin sulfonates, (2) , that is, substances prepared by reacting olefins, especially C10-C20 alpha-olefins, with sulfur trioxide, followed by neutralization and hydrolysis of the reaction product; sodium and potassium C7-C12 dialkyl succinate sulfonates, (3); chain Alkane monosulfonates, (4), such as those obtained by reacting C8-C20 alpha-olefins with sodium bisulfite and by reacting paraffins with SO2 and C12, followed by alkaline hydrolysis to form atactic sulfonates; Alpha-sulfo fatty acid salts or esters, (10); sodium alkylglyceryl sulfonates, (11), especially those ethers of higher alcohols derived from tallow or coconut oil and of synthetic alcohols derived from petroleum; alkyl Or alkenyl sulfate, (15), which can be primary or secondary, saturated or unsaturated, branched or unbranched. If branched, the compounds can be random or regular, if secondary they preferably have the formula: CH3(CH2)x(CHOSO3-M+)CH3 or CH3(CH2)y(CHO SO3-M+)CH2CH3, wherein x and (y+1) are integers of at least 7, preferably at least 9, and M is a water-soluble cation, preferably sodium. If unsaturated, sulphates such as oleyl sulphate are preferred, while sodium and ammonium alkyl sulphates, especially those prepared by sulphating C8-C18 alcohols, such as those produced from tallow or coconut oil, are also useful; Also preferred are alkyl or alkenyl ether sulfates, (16), especially ethoxysulfates with about 0.5 mol or more ethoxylation, preferably 0.5-8; alkyl ether carboxylates, (19), Especially EO1-5 ethoxy carboxylates; soaps or fatty acids (21), preferably more water-soluble types; surfactants of the amino acid type, (23), such as sarcosinates, especially oleyl sarcosinates ; Phosphates, (26); Alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30), especially ethoxylates "AE", including so-called narrow peak alkyl Ethoxylates and C6-C12 alkylphenol alkoxylates and products of aliphatic primary or secondary straight or branched C8-C18 alcohols with ethylene oxide, usually 2-30 EO; N-alkyl polyhydroxy fatty acids Amides, especially C12-C18N-methylglucamide, (32), see WO9206154, and N-alkoxypolyhydroxy fatty acid amides, such as C10-C18N-(3-methoxypropyl)glucamide, Whereas N-propyl to N-hexyl C12-C18 glucamides can be used for low foaming; alkyl polyglycosides, (33); amine oxides, (40), preferably alkyldimethylamine N-oxides and their dihydrate; sultaine, (43); betaine (44); and distructural surfactants.

Suitable levels of the anionic detersive surfactants herein are from about 1% to about 50% or more, preferably from about 2% to about 30%, more preferably from about 5% to about 20%, by weight of the detergent compositions.

Suitable levels of nonionic detersive surfactants herein are from about 1% to about 40%, preferably from about 2% to about 30%, more preferably from about 5% to about 20%.

Desirable weight ratios of anionic:nonionic surfactants in the mixture include 1.0:9.0 to 1.0:0.25, preferably 1.0:1.5 to 1.0:0.4.

Suitable levels of cationic detersive surfactants herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although higher levels, e.g. up to about 30% or higher, are especially useful for nonionic Surfactants: Cationic surfactants (ie, limited or no anionic surfactants) in formulations.

Amphoteric or zwitterionic detersive surfactants, when present, are generally used at levels of from about 0.1% to about 20% by weight of the detergent composition, and will usually be limited to about 5% or less, especially in amphoteric surfactants. When the agent is expensive.

Detergency Enzymes - Enzymes are preferably included in the detergent compositions of the present invention for a variety of purposes, including removal of protein-based, carbohydrate-based or triglyceride-based stains from soil carriers, in order to prevent short-circuiting in fabric washes Efficient dye transfer, and for fabric restoration. Recent enzyme disclosures in detergents useful in the present invention include bleach/amylase/protease combinations (EP755999A, EP756001A, EP756000A), chondroitinase (EP747469A), protease variants (WO96/28566A, WO96/28557A, WO96/28556A, WO96/25489A), xylanase (EP709452A), keratinase (EP747470A), lipase (GB2297979A, WO96/16153A, WO96/12004A, EP698659A, WO96/16154A), cellulase (GB2294269A, WP96 /27649A, GB2303147A), thermitase (WO96/28558A). More generally, suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, xylanases, keratinases, chondroitinases, thermitases, cutinases, and mixtures thereof, with any suitable sources such as plant, animal, bacterial, fungal and yeast origin. Their preferred selection is influenced by factors such as pH-activity and/or stability optima, thermostability and stability to active detergents, builders and the like. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Suitable enzymes are also found in US5677272, 5679630, 5703027, 5703034, 5705464, 5707950, 5707951, 5710115, 5710116, 5710118, 5710119 and 5721202.

As used herein, "detergency enzyme" refers to any enzyme having a detergency, stain removal or other benefit in laundry, hard surface cleaning and personal care detergent compositions. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred are amylases and/or proteases, both currently commercially available and improved, although improved to some degree, although increasingly compatible with bleaches through continuous improvement Sensitivity to bleach deactivation.

Enzymes are typically incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removing, soil removing, whitening, deodorizing or freshness enhancing effect on soiled substrates such as fabrics, dishware and the like. Typical amounts of active enzyme are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, per gram of detergent composition for current commercial formulations. In other words, the compositions of the invention generally comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight of the commercial formulation. The level of protease in such commercial formulations should generally be sufficient to produce 0.005-0.1 Anson Units (AU) of activity per gram of composition. For some detergents it may be desirable to increase the active enzyme content of commercial formulations in order to reduce the total amount of non-catalytically active material to improve spotting/filming or other end results. Higher active levels are also desirable in highly concentrated detergent formulations.

Suitable examples of proteases are subtilisins obtained from special strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease obtained from a strain of Bacillus having maximal activity over the entire pH range of 8-12 was developed by Novo Industries A/S (Denmark) and sold as ESPERASE®, hereinafter "Novo". The preparation of this and similar enzymes is described in GB1243784 to Novo. Other suitable proteases include ALCALASE_ and SAVINASE_ available from Novo and MAXATASE_ available from International Bio-Synthetics, Inc (Netherlands); and Protease A described in EP130756A published January 9, 1985, and Protease B described in EP303761A published on the 28th and EP130756A published on January 9, 1985. See also the high pH protease from Bacillus NCIMB 40338 described in WO9318140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include the enzymes in WO9510591A to Procter & Gamble. If desired, proteases with reduced adsorption and improved hydrolysis are available as described in WO9507791 to Procter & Gamble. WO9425583 to Novo describes a recombinant trypsin-like protease suitable for use in the detergents of the present invention.

More specifically, an especially preferred protease known as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, as described in Genencor International WO 95/10615, published April 20, 1995, It is achieved by substituting various amino acid residues with different amino acids at positions corresponding to +76 in the above-mentioned carbonyl hydrolases, and preferably also in combination with substitutions corresponding to those selected from the group consisting of the numbering +99, +101, + 103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, One or more amino acid residues at positions +216, +217, +218, +222, +260, +265 and/or +274 are derived from precursor carbonyl hydrolases.

Useful proteases are also described in the following PCT publications: WO95/30010, The Procter & Gamble Company, published November 9, 1995; WO95/30011, The Procter & Gamble Company, published November 9, 1995; WO95/29979 of The Procter & Gamble Company published on 9th.

Amylases suitable for use in the present invention include, for example, alpha-amylases described in GB1296839 to Novo; RAPIDASE® from International Bio-Synthetics, Inc and TERMAMYL® from Novo, FUNGAMYL® from Novo is particularly useful. Enzyme engineering for improved stability, such as oxidative stability, is known. See, eg, J. Biological Chem, Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the present invention may utilize amylases having improved stability in detergents, especially improved oxidative stability relative to the 1993 reference point of commercially used TERMAMYL®. These preferred amylases of the present invention are characterized as "stability-increased" amylases characterized at least by the reaction of hydrogen peroxide/tetraacetyl Oxidative stability of ethylenediamine; as thermal stability at normal wash temperatures such as about 60°C; or as having a measurable improvement in alkali stability at a pH of about 8-11 (compared to the aforementioned reference point starch Enzymes are measured). Stability can be tested using any of the assay methods disclosed in the prior art, eg see WO9402597. Stability-improved amylases are available from Novo or Genencor International. A highly preferred amylase of the present invention has in common that it is derived using site-directed mutagenesis from one or more Bacillus amylases, particularly from Bacillus α-amylases, regardless of whether one, two or Are multiple amylase strains immediate precursors. Amylases having increased oxidative stability relative to the reference amylases mentioned above are preferably used, especially for use in bleaching, more preferably oxygen bleaching detergent compositions as opposed to chlorine bleaching, according to the invention. Such preferred amylases include (a) amylases according to the aforementioned WO 9402597, Novo, February 3, 1994, which can be further illustrated by a mutant wherein alanine or threonine is used, It is preferred to substitute threonine at position 197 of a Bacillus licheniformis alpha-amylase called TERMAMYL_, or a homologous position variant of a similar parent amylase such as Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus. Methionine residues; (b) as described by Genencor International in a paper entitled "Antioxidant α-amylases" presented by C. Mitchinson to the 207th Annual Meeting of the American Chemical Society, March 13-17, 1994 Amylases with increased stability. It is mentioned that bleach in automatic dishwashing detergents inactivates alpha-amylases, but Genencor produces improved oxidative stability amylases from Bacillus licheniformis NCIB8061. Methionine (Met) proved to be the most easily modifiable residue. Met was substituted one at a time at positions 8, 15, 197, 256, 304, 366 and 438 to obtain specific mutants, particularly important M197L and M197T, with the M197T variant being the most stably expressed variant. Stability is measured in CASCADE_ and SUNLIGHT_; (c) particularly preferred amylases of the invention include amylase variants with additional modifications in the immediate parent as described in WO9510603A and as DURAMYL_ by assignee Novo get. Other particularly preferred amylases with increased oxidative stability include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other amylase with increased oxidative stability may be used, for example derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzymatic modifications can be made, see WO9509909A to Novo.

Other amylases include those described in WO95/26397 and in co-pending application PCT/DK96/00056 by Novo Nordisk. Particular amylases suitable for use in the detergent compositions of the present invention include alpha-amylases characterized by having a specific activity at least 25% specific activity of α-amylase as determined by Phadebas-α-amylase activity test. (The Phadebas-α-amylase activity assay is described on pages 9-10 of WO/95/26397). Also included are alpha-amylases that are at least 80% homologous to the amino acid sequences shown in the SEQ ID sequence listings listed in the references. These enzymes are preferably incorporated into laundry detergent compositions at levels of from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases used in the present invention include bacterial and fungal types, preferably having an optimum pH of 5-9.5. US4435307, March 6, 1984 by Barbesgoard et al. discloses suitable fungal cellulase obtained from Humicola insolens or Humicola strain DSM1800 or from a cellulase 212 producing fungus belonging to the genus Aeromonas, and from marine Cellulase extracted from the hepatopancreas of the mollusk Dolabella Auricula Solander. GB-A-2075028, GB-A-2095275 and DE-OS-2247832 also disclose suitable cellulases. CAREZYME_ and CELLUZYME_ (Novo) are particularly useful, see also WO9117243 to Novo.

Lipases suitable for use in detergents include lipases obtained from microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 as disclosed in GB1372034. See also Japanese Patent Application No. 53,20487, published February 24, 1978, available from Amano Pharmaceutical Co. Ltd. (Nagoya, Japan) under the trade name Lipase P "Amano" or " Amano-P". Other suitable commercial lipases include Amano-CES, a lipase from Chromobacter viscosum such as Dhromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co. (Tagata, Japan); commercially available from U.S. Biochemical Corp. (US) and Disoynth (Netherlands) the obtained Chromobacterviscosum lipase; and the lipase obtained from Pseudomonas gladioli. LIPOLASE® enzyme derived from Humicolalanuginosa and commercially available from Novo (see also EP341947) is a preferred lipase for use in the present invention. Peroxidase-stable lipase and amylase variants are described in WO9414951A to Novo. See also WO9205249 and RD94359044.

Cutinases suitable for use in the present invention are described in WO8809367A to Genencor.

Peroxidases can be used in combination with oxygen sources such as percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or to prevent the transfer of dyes or pigments removed from the substrate during washing operations to the among other substrates in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Detergent compositions containing peroxidase are disclosed in WO89099813A, Novo, October 19, 1989 and WO8909813A, Novo.

WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139 to McCarty et al. issued January 5, 1971 also disclose various enzyme materials and their incorporation into synthetic detergent compositions. Enzymes are further disclosed in US Pat. No. 4,101,457, Place et al., issued July 18, 1978, and US Pat. US Patent 4,261,868, Hora et al., issued April 14, 1981, discloses enzyme materials for use in liquid laundry formulations, and their incorporation into such formulations. Enzymes for use in detergents can be stabilized in a variety of ways. Enzyme stabilization techniques are disclosed and enumerated in US3600319 issued August 17, 1971 by Gedge et al. and EP199405 and EP200586 issued October 29, 1986 by Venegas. Enzyme stabilization systems are also described eg in US3519570A. WO9401532A to Novo describes a useful Bacillus sp. AC13 capable of deriving proteases, xylanases and cellulases.

Builders - Detergent builders are preferably included in the compositions of the present invention, for example to help control mineral, especially calcium and/or magnesium hardness in the wash water or to help remove and/or magnesium from surfaces or suspended particulate dirt and sometimes provide alkaline and/or buffering action. In solid formulations, builders are sometimes used as adsorbents for surfactants. Additionally, certain compositions can be formulated with organic or inorganic fully water-soluble builders, depending on the intended use.

Suitable silicate builders include water-soluble and hydrated solid types, including those having a chain, layered or three-dimensional structure as well as amorphous solid silicates or other types such as silicon especially suitable for unstructured liquid detergents. salt. Alkali metal silicates are preferred, especially those liquids and solids having a SiO ₂ :Na ₂ O ratio in the range of 1.6:1 to 3.2:1, including the solid hydrated 2- ratio silicates; and phyllosilicates such as those described in US 4,664,839, HP Rieck, issued May 12,1987. Na SKS-6, sometimes abbreviated "SKS-6" is a crystalline layered aluminum-free delta- _Na2SiO5 form silicate sold by Hoechst, _especially preferred for use in granular laundry compositions. See the preparation methods described in DE-A-3417649 and DE-A-3742043. Other phyllosilicates may also or additionally be used, such as silicates having the general formula _{NaMSixO2x +1.yH2O ,} where M is sodium or hydrogen and x is a number from 1.9 to 4, preferably 2, And y is a number of 0-20, preferably 0. Phyllosilicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 in the alpha, beta, and gamma phyllosilicate forms, respectively. Other silicates can also be used, such as magnesium silicate, which can be used as a crisping agent in granular formulations, as a stabilizer for bleaches, and as a component in suds control systems.

Also suitable for use in the present invention are synthetic crystalline ion exchange materials having a chain structure or hydrates thereof, and components in the form of anhydrides as described in US5427711 issued June 27, 1995 to Sakaguchi et al represented by the general formula : xM ₂ O.ySiO ₂ .zM'O, wherein M is sodium and/or potassium, M' is calcium and/or magnesium; y/x is 0.5-2.0 and z/x is 0.005-1.0.

Aluminosilicate builders, such as zeolites, are especially suitable for use in granular detergents, but can also be added to liquids, pastes or gels. Suitable for use in the present invention are those having the following empirical formula: [M _z (AlO ₂ ) _z .(SiO ₂ ) _v ].xH ₂ O, where z and v are integers of at least 6, and the molar ratio of z and v The ratio is in the range of 1.0-0.5, and x is an integer of 15-264. Aluminosilicates may be crystalline or amorphous, and may be naturally occurring or synthetically derived. US 3,985,669, Krummel et al., issued October 12, 1976, describes a process for the production of aluminosilicates. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as zeolite A, zeolite P (B), zeolite X and the so-called zeolite MAP which differs to some extent from zeolite P. Natural types can be used, including clinoptilolite. Zeolite A has the following formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O, where x is 20-30, especially 27. Dehydrated zeolites (x = 0-10) may also be used, the aluminosilicate preferably having a particle size of 0.1-10 microns in diameter.

Detergent builders instead of or in addition to the silicates and aluminosilicates described herein may optionally be included in the compositions of the present invention, for example to help control minerals, especially calcium, in the wash water. And/or magnesium hardness may help remove particulate dirt from surfaces. Builders can function by various mechanisms, including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by providing surfaces that are more conducive to the deposition of hardness ions than the surface of the article being washed. The amount of builder used can vary widely depending on the end use and physical form of the composition. Built detergents generally contain at least about 1% builder. Liquid formulations generally contain from about 5% to about 50%, more typically from 5% to 35%, by weight of builder. Granular formulations generally contain from about 10% to about 80%, more typically 15% to 50%, by weight of the composition, of builder. However, this is not meant to exclude lower or higher levels of builders. For example, certain detergent additives or high surfactant formulations can be unbuilt.

Builders suitable for use herein may be selected from phosphates and polyphosphates, especially sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonic acids other than sodium carbonate or sodium sesquicarbonate Salt minerals; organic mono-, di-, tri- and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium or alkanolammonium salts; and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types; and phytic acid. These can be supplemented by borates, such as borates for pH buffering purposes, or sulfates, especially sodium sulfate, and any other fillers or carriers that are useful for stabilizing surfactants and/or builder-containing detergents The engineering of the composition is important.

Builder mixtures, sometimes called "builder systems," may be used, which generally contain two or more conventional builders, optionally supplemented with chelating agents, pH buffers, or fillers, although some of the latter substances are in When describing the amount of a substance, it is usually stated separately. With regard to the relative amounts of surfactant and builder in the detergents of the present invention, preferred builder systems are generally formulated at a surfactant to builder weight ratio of from about 60:1 to about 1:80. Certain preferred laundry detergents have said ratios of 0.90:1.0 to 4.0:1.0, more preferably 0.95:1.0 to 3.0:1.0.

Phosphorus-containing detergent builders include, but are not limited to, alkali metal, ammonium, and alkane polyphosphates (specifically tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates) and phosphonates, when permitted by regulation. Alcohol ammonium salt.

Suitable carbonate builders include alkaline earth and alkali metal carbonates, which are described in German Patent Application No. 2321001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sesqui Sodium carbonate and other carbonate minerals such as trona or any conventional double salt of sodium and calcium carbonate, for example having the composition 2Na ₂ CO ₃ .CaCO ₃ when anhydrous, and calcium carbonate, including calcite, wen Calcite and vaterite, especially the high surface area forms relative to dense calcite, can be used, for example, as seed crystals or in synthetic detergent bars.

Suitable "organic detergent builders" for use with the alkylaryl sulfonate surfactant systems described herein include polycarboxylate compounds, including dicarboxylates of water-soluble nonsurfactants and Tricarboxylates. The more common builder polycarboxylates have a number of carboxylate groups, preferably at least 3 carboxylate groups. Carboxylate builders can be formulated in acid form, partially neutralized, neutralized or overbased form. When used in salt form, alkali metals, such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylate builders such as oxydisuccinates, see US Pat. "TMS/TDS" builders in US4663071, Bush et al., issued May 5; and other ether carboxylates, including cyclic and alicyclic compounds, as described in US3923679, 3835163, 4158635, 4120874 and 4102903 of those compounds.

Other suitable organic detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonate carboxymethyloxysuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; and mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrates, such as citric acid and its soluble sodium salt, are important carboxylate builders for heavy duty liquid detergents due to their renewable resource availability and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolites and/or layered silicates. Oxydisuccinates are also particularly useful in such compositions and mixtures.

Where permitted, alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate may be used, especially in bar formulations for hand laundry operations. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those described in US Pat. , they will have the desired antifouling properties.

Certain detersive surfactants or their short chain homologues also have builder action. For formulation purposes, these materials are summarized as detersive surfactants when they have a surfactant action. Such preferred materials for builder functionality are exemplified by the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US Patent 4,566,984, Bush, issued January 28, 1986 illustrate. Succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristyl succinate, cetyl succinate, 2-dodecenyl succinate (preferred), 2-pentadecyl alkenyl succinate, etc. Lauryl succinate is described in European Patent Application 86200690.5/0200263, published November 5, 1986. Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be incorporated into the composition as surfactant/builder substances alone or together with the above-mentioned builders, especially citrate and/or succinate builders To provide additional builder activity. Other suitable polycarboxylates are described in US Pat. See also US3723322 to Diehl.

Other types of inorganic builder materials that can be used have the formula: (M _x ) _i Ca _y (CO ₃ ) _z where x and i are integers from 1 to 15, y is an integer from 1 to 10, and z is 2 An integer of -25, M _i is a cation, at least one of which is a water-soluble cation, satisfying the equation ∑ _i =1-15 (the valence of x _i multiplied by M _i )+2y=2z, making the chemical formula neutral or "balanced"The" charge. These builders are referred to herein as "mineral builders" and examples of such builders, their use and methods of preparation can be found in US5707959. Another suitable class of inorganic builders are magnesium silicates, see WO 97/0179.

Oxygen bleach:

Preferred compositions of the invention contain "oxygen bleach" as part or all of the laundry or wash aid material. The oxygen bleach used in the present invention can be any oxidizing agent known for use in laundry, hard surface cleaning, automatic dishwashing or denture cleaning applications. Oxygen bleaches or mixtures thereof are preferred, although other oxidant bleaches such as oxygen, enzymatically catalyzed hydrogen peroxide generating systems or hypohalites, eg chlorine bleaches such as hypochlorite, may also be used.

Common oxygen bleaches of the peroxygen type include hydrogen peroxide, inorganic peroxyhydrates, organic peroxyhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- or diperoxyacids. They may be peroxycarboxylic acids, peroximidic acid, amidoperoxycarboxylic acids or their salts, including calcium, magnesium or mixed cation salts. The various peracids are available in free form and as precursors known as "bleach activators" or "bleach boosters" which, when combined with a source of hydrogen peroxide, are perhydrolyzed to liberate the corresponding peracids.

Also used as oxygen bleaches are inorganic peroxides such as Na2O2, superoxides such as KO2, organic hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide, and inorganic peroxyacids and their salts, such as peroxosulfates, especially potassium peroxodisulfate, and more preferably potassium peroxymonosulfate, including the commercial triple salt form sold by DuPont as OXONE, also in any equivalent commercially available form, For example CUROX from Akzo or CAROAT from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may also be used, especially as additives rather than as primary oxygen bleaches.

Mixed oxygen bleach systems are generally useful, such as mixtures of any oxygen bleach with known bleach activators, organic catalysts, enzyme catalysts, and mixtures thereof, which may additionally contain known in the art Brighteners, Photobleaches and Dye Transfer Inhibitors.

The preferred oxygen bleaches mentioned above include peroxohydrates, sometimes referred to as peroxyhydrates or peroxohydrates. These are organic or more commonly inorganic salts that readily release hydrogen peroxide. Peroxyhydrates are the most common examples of "hydrogen peroxide source" species and include perborates, percarbonates, perphosphates and persilicates. Suitable peroxyhydrates include sodium carbonate peroxyhydrate and equivalent commercial "percarbonate" bleaches, and any so-called sodium perborate hydrate, "tetrahydrate" and "monohydrate" being preferred , although sodium pyrophosphate peroxyhydrate can also be used. Many of these peroxyhydrates are available in processed form with coatings, such as silicates and/or borates and/or waxy substances and/or surfactants, or in granular geometric forms, such as dense spheres, It improves storage stability. For example organic peroxyhydrates, urea peroxyhydrates are also useful in the present invention.

Percarbonate bleaches include, for example, dry particles having an average particle size in the range of about 500 microns to about 1000 microns, wherein not more than about 10 percent by weight of said particles are smaller than about 200 microns, and not more than about 1000 microns by weight. About 10% by weight of the particles are larger than about 1250 microns. Percarbonate and perborate are commercially available from various sources such as FMC, Solvay and Tokai Denka.

Organic percarboxylic acids useful herein as oxygen bleaches include magnesium monoperoxyphthalate hexahydrate, available from Interox, m-chloroperbenzoic acid and its salts, 4-nonylamino-4-oxoperoxy Butyric acid and diperoxydodecanedioic acid and their salts. Such bleaching agents are disclosed in US 4,483,781, US Patent Application 740,446, filed June 3, 1985 by Burns et al., EP-A 133,354, published February 20, 1985, and US 4,412,934. Organic percarboxylic acids useful in the present invention include materials containing one, two or more peroxy groups, which may be aliphatic or aromatic. Highly preferred oxygen bleaches also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in US4634551.

An extensive and exhaustive description of useful oxygen bleaches, including inorganic peroxyhydrates, organic peroxyhydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- or diperoxyacids, peroxyacids, Oxycarboxylic acids, peroxyimino acids, amidoperoxycarboxylic acids or their salts, including calcium, magnesium or mixed cation salts.

Other useful peracids and bleach activators are the family of imino peracids and imino bleach activators. These include phthalyliminoperoxycaproic acid and related arylimino-substituted and acyloxynitrogen derivatives.关于该化合物、制备方法和它们在洗衣组合物，包括颗粒和液体中的加入参见US5487818、US5470988、US5466825、US5419846、US5415796、US5391324、US5328634、US5310934、US5279757、US5246620、US5245075、US5294362、US5423998、US5208340、US5132431 and US5087385.

Useful diperoxyacids include, for example, 1,12-diperoxydodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybasyl acid, diperoxysebacic acid and Peroxyisophthalic acid, 2-decyl diperoxybutane-1,4-dioic acid and 4,4'-sulfonyl diperoxybenzoic acid.

More generally, the terms "hydrophilic" and "hydrophobic" as used herein in relation to any oxygen bleach, especially peracids and in relation to bleach activators, are in the first instance according to whether a given oxygen bleach Effectively performs bleaching of fugitive dyes in solution to avoid graying and discoloration of fabrics and/or to remove more hydrophilic stains such as tea, wine and grape juice - in which case it is called "hydrophilic". An oxygen bleach or bleach activator is said to be "hydrophobic" when it has significant stain removal, whiteness improvement or cleaning benefits on dull, greasy, carotenoid or other hydrophobic soils. The term is also used when a peracid or bleach activator is used in combination with a source of hydrogen peroxide. Existing commercial benchmarks for the hydrophilic properties of oxygen bleach systems are: TAED or peracetic acid for hydrophilic bleaches and NOBS or NAPAA the corresponding benchmarks for hydrophobic bleaches. The terms "hydrophilic", "hydrophobic" and "water soluble" in relation to oxygen bleaches, including peracids and by extension bleach activators, are also used more narrowly in the literature. See especially Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4, pp. 284-285. This reference provides a set of criteria based on chromatographic retention time and critical micelle concentration for identifying and/or characterizing preferred subclasses of hydrophobic, hydrophilic and water-soluble oxygen bleaches and bleach activators for use in the present invention .

bleach activator

Bleach activators useful herein include amides, imides, esters and anhydrides. There is usually at least one substituted or unsubstituted acyl moiety covalently attached to a leaving group, as in structure R-C(O)-L. In a preferred form of use, the bleach activator is combined with a source of hydrogen peroxide, such as perborate or percarbonate, in a single product. The single product conveniently produces an aqueous solution of the percarboxylic acid corresponding to the bleach activator in situ (ie during the wash). The product itself may be aqueous, such as a powder, provided the water is of such controlled quantity and fluidity that storage stability is acceptable. Additionally, the product can be an anhydrous solid or liquid. In another approach, bleach activators or oxygen bleaches are added to pretreatment products, such as stains; soiled, pretreated soil carriers can then be subjected to other treatments, such as a source of hydrogen peroxide. For the above bleach activator structure RC(O)L, the atom in the leaving group attached to the peracid-forming acyl moiety RC(O)- is most commonly O or N. Bleach activators may be uncharged, positively or negatively charged peracid forming moieties and/or uncharged, positively or negatively charged leaving groups. One or more peracid forming moieties or leaving groups may be present. See for example the bis-(peracid-carbon) systems of US5595967, US5561235, US5560862, or US5534179. Mixtures of suitable bleach activators may also be used. Bleach activators can be substituted by electron donating or electron releasing groups in the leaving group or in the peracid forming moiety, modifying their reactivity and making them more or less suitable for a particular pH or wash conditions. For example, electron withdrawing groups, such as NO2, improve the efficacy of bleach activators intended for mild pH (eg, about 7.5 to about 9.5) wash conditions.

An extensive and detailed description of suitable bleach activators and suitable leaving groups and how to determine a suitable activator can be found in US5686014 and US5622646.

Cationic bleach activators include quaternized urethane-, quaternized carbonate-, quaternized ester- and quaternized amide-types, providing various cationic peroximidic acid, peroxycarbonic acid or peroxycarboxylic acid. If quaternized derivatives are undesirable, similar but non-cationic blends of bleach activators are obtained. More specifically, cationic activators include the quaternary ammonium substituted activators of WO96-06915, US4751015, 4397757, EP-A-284292, EP-A-331229 and EP-A-03520. Also useful are the cationic nitriles disclosed in EP-A-303520 and EP458396 and 464880. Other nitrile types contain electron withdrawing substituents as described in US5591378.

Disclosures of other bleach activators include GB836998, 864798, 907356, 1003310 and 1519351; DE3337921; Phenolsulfonate esters of chain acylamino acids disclosed in . Suitable bleach activators include any acylated diamine type, which may be hydrophilic or hydrophobic in nature.

Of the above classes of bleach activators, preferred classes include esters, including acylphenol sulfonates, acyl alkylphenol sulfonates, or acyl ishenyl sulfonates (OBS leaving groups); acyl amides; and quaternary ammonium substituted peroxyacid precursors, including cationic nitriles.

Preferred bleach activators include N,N,N'N'-tetraacetylethylenediamine (TAED) or any close related species thereof, including triacetyl or other asymmetric derivatives. TAED and acylated carbohydrates such as sucrose pentaacetate and tetraacetylxylose are preferred hydrophilic bleach activators. Depending on the application, liquids like phenyl benzoate, acetyl triethyl citrate, also have some effect.

Preferred hydrophobic bleach activators include nonanoyloxybenzenesulfonate (NOBS or SNOBS), N-(alkanoyl)aminoalkanoyloxybenzenesulfonate, such as 4-[N-(nonanoyl)amino Hexanoyloxy]-benzenesulfonate or (NACA-OBS), as described in US5534642 and EPA355384A1, substituted amides of the type described in detail below, such as activators related to NAPAA and bleaching involving certain imino peracids Activators of agents as described in US5061807 issued October 29, 1991, assigned to HoechstAktiengesellschaft of Frankfurt, Germany, and Japanese Laid-Open Patent Application (Kokai) No. 4-28799.

Another group of peracids and bleach activators according to the invention are those derived from acyclic iminoperoxycarboxylic acids and their salts, see US5415576, and those derived from cyclic iminoperoxycarboxylic acids and their salts, see US5061807, 5132431, 5654269, 5246620, 5419864 and 5438147.

Other suitable bleach activators include sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate, 4-methyl-3-benzene Sodium formyloxybenzoate (SPCC), trimethylammonium toluoyloxy-benzenesulfonate, or sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (STHOBS).

Bleach activators may be used in amounts of up to 20% by weight of the composition, preferably from 0.1% to 10%, although higher levels, 40% or more are acceptable, for example in the form of highly concentrated bleach additive products or A form intended for automatic metering of appliances.

Highly preferred bleach activators for use herein are amide substituted, a broad and detailed description of these activators can be found in US5686014 and US5622646.

Other useful activators disclosed in US4966723 are of the benzoxazine type, for example a _C6H4 ring fused to the 1,2- _position of the group -C(O)OC(R1)=N-. Highly preferred activators for benzoxazines are:

Depending on the activator and the exact application, good bleaching results can be obtained from bleach systems having a use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. For example, activators with electron-withdrawing moieties are typically used in the near neutral or sub-neutral pH range, and bases and buffers can be used to achieve this pH.

Acyl lactam activators are very useful in the present invention, especially acyl caprolactams (see eg WO94-28102A) and acyl valerolactams (see US5503639). See also US4545784 which discloses acyl caprolactams including benzoyl caprolactam adsorbed in sodium perborate. In certain preferred embodiments of the present invention, NOBS, lactam activators, imide activators, or amide functional activators, especially the more hydrophobic derivatives, need to be combined with a hydrophilic bleach activator, such as TAED, usually in the form of Hydrophobic activator: TAED 1:5-5:1, preferably combined in a weight ratio of about 1:1. Other suitable lactam activators are alpha-modified, see WO 96-22350A1, 25.07.1996. Lactam activators, especially the more hydrophobic types, need to be combined with TAED, usually amide-derivatized or caprolactam activators:TAED in a weight ratio of 1:5-5:1, preferably about 1:1. See also the bleach activators having a cyclic amidine leaving group disclosed in US5552556.

Other non-limiting examples of activators useful in the present invention are found in US4915854, US4412934 and 4634551. Hydrophobic activators nonanoyloxybenzenesulfonate (NOBS) and hydrophilic tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used.

Other activators useful in the present invention include those in US5545349.

Transition metal bleach catalysts:

If desired, the bleaching compound can be catalyzed with a manganese compound. Such compounds are known in the art and include, for example, those disclosed in US5246621, US5244594, US5194416, US5114606, and EP549271A1, 549272A1, 544440A2 and 544490A1 and PCT application PCT/IB98/00298 (Attorney Docket No. 6527X), PCT Manganese-based catalysts in /IB98/00299 (Attorney Docket No. 6537), PCT/IB98/00300 (Attorney Docket No. 6525XL&) and PCT/IB98/00302 (Attorney Docket No. 6524L#). Preferred examples of such catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4 , 7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III -Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7- Triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal based bleach catalysts include those disclosed in US4430243, 5114611, 5622646 and 5686014. The use of manganese and various complexing ligands to enhance bleaching performance is also reported in the following US Patent Nos.

Cobalt bleach catalysts for use in the present invention are known and described, for example, in ML Tobe. "Alkaline hydrolysis of transition metal complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94. The most preferred cobalt catalyst for use in the present invention is cobalt pentaamine acetate having the formula [Co( _NH3 ) _5OAc ] _Ty , where "OAc" denotes an acetate moiety and "Ty" is an anion, especially cobalt Pentaamine acetate chloride, [Co(NH ₃ ) ₅ OAc]Cl ₂ ; and [Co(NH ₃ ) ₅ OAc](OAc) ₂ ; [Co(NH ₃ ) ₅ OAc](PF ₆ ) ₂ ; [Co(NH ₃ ) ₅ OAc](SO ₄ ); [Co(NH ₃ ) ₅ OAc](BF ₄ ) ₂ ; [Co(NH ₃ ) ₅ OAc](NO ₃ ) ₂ (referred to herein as "PAC "). These cobalt catalysts are readily prepared by known methods, such as those disclosed in the Tobe article supra and references cited therein, and in US Patent 4,810,410, Diakun et al., issued March 7,1989.

The compositions of the present invention may also suitably include transition metal complexes as polycyclic rigid ligands as bleach catalysts. The phrase "macrocyclic rigid ligand" is sometimes abbreviated "MRL". A useful MRL is [MnByclamCl2], where "Bcyclam" is (5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane). See PCT applications PCT/IB98/00298 (Attorney Docket No. 6527X), PCT/IB98/00299 (Attorney Docket No. 6537), PCT/IB98/00300 (Attorney Docket No. No.6524L#). The amount used is a catalytically effective amount, suitably about 1 ppb or more, such as up to about 99.9%, more usually about 0.001 ppm or more, preferably about 0.05 ppm to about 500 ppm (wherein "ppb" means by weight parts per billion, "ppm" means parts per million by weight).

As a practical matter, but not by way of limitation, the compositions and washing methods of the present invention can be adjusted to provide at least about 0.01 ppm active bleach catalyst material in the aqueous medium, preferably from about 0.01 ppm to about 25 ppm in the wash liquor, more preferably From about 0.05 ppm to about 10 ppm, most preferably from about 0.1 ppm to about 5 ppm bleach catalyst material. To achieve this level of wash liquor for automatic dishwashing processes, typical compositions of the present invention will contain from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, by weight of the detergent composition, of a bleach catalyst, especially manganese or cobalt catalyst.

Enzymatic source of hydrogen peroxide

Using a different route than the above bleach activators, another suitable hydrogen peroxide generating system is the combination of C1-C4 alkanol oxidase and C1-C4 alcohol, especially methanol oxidase (MOX) and ethanol. This combination is disclosed in WO94/03003. Other enzymatic substances involved in bleaching, such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalases and their synergists or more commonly inhibitors are available as an optional component of the compositions of the present invention.

Oxygen Transfer Agents and Precursors

Also suitable for use herein are any known organic bleach catalysts, oxygen transfer agents or precursors thereof. They include the compound itself and/or its precursors, such as any suitable ketone for the production of dioxirane and/or any dioxirane precursor or heteroatom-containing analogue of dioxirane, such as For sulfoimine R1R2C=NSO2R3, see EP446982A published in 1991 and sulfonyloxaziridine, see EP446981A published in 1991. Preferred examples of such materials include hydrophilic or hydrophobic ketones, especially in combination with monoperoxysulfate to generate dioxirane in situ and/or imines as described in US5576282 and references therein. Oxygen bleaches preferably used in combination with the oxygen transfer agent or precursors thereof include percarboxylic acids and salts, percarbonic acids and salts, permonosulfuric acid and salts and mixtures thereof. See also US5360568, US5360569, US5370826 and US5442066.

Although in storage in moisture, air (oxygen and/or carbon dioxide) and trace metals (especially rust or single salts or colloidal oxides of transition metals) and when exposed to light oxygen bleach systems and/or their precursors Easy to decompose, the stability can be improved by adding common chelating agents and/or polymeric dispersants and/or a small amount of antioxidants to the bleaching system or product. See eg US5545349. Antioxidants are commonly added to detergent components ranging from enzymes to surfactants. Their presence is not inconsistent with the use of oxidizing agent bleaches; for example the addition of phase carriers can be used to stabilize the apparently incompatible combination of enzymes and, on the one hand, antioxidants and, on the other hand, oxygen bleaches. Although generally known substances can be used as antioxidants, see for example US5686014, 5622646, 5055218, 4853143, 4539130 and 4483778. Preferred antioxidants are 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydroquinone and D,L-alpha-tocopherol.

Polymeric Soil Release Agents - The compositions of the present invention may optionally contain one or more soil release agents. Polymeric soil release agents are characterized by having both a hydrophilic portion which makes the surface of hydrophobic fibers such as polyester and nylon hydrophilic; and a hydrophobic portion which deposits on the hydrophobic fibers and sticks to them during the wash cycle. attached thereto and thus serve as an anchor point for the hydrophilic part. This ensures that stains produced after treatment with the stain remover can be easily washed away during the subsequent washing process.

If used, soil release agents will generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, by weight of the compositions.

All of the following references herein describe soil release polymers suitable for use in the present invention. US5691298 of Gosselink et al. issued on November 25, 1997, US5599782 of Pan et al. issued on February 4, 1997, US5415807 of Gosselink et al. issued on May 16, 1995, Morrall et al. of January 26, 1993 US5182043, US4956447 issued on September 11, 1990 by Gosselink et al., US4976879 issued by Maldonado et al. on December 11, 1990, US4968451 issued by Scheibel et al. on November 6, 1990, Borcher issued on May 15, 1990 US4925577, US4861512 of Gosselink issued on August 29, 1989, US4877896 of Maldonado, etc. issued on October 31, 1989, US4702857 of Gosselink, etc. issued on October 27, 1987, US4702857 issued on December 8, 1987 US4711730 of Gosselink et al, US4721580 of Gosselink issued on January 26, 1988, US4000093 of Nicol et al issued on December 28, 1976, US3959230 of Hayes issued on May 25, 1976, US3959230 of Hayes issued on July 8, 1975 US3893929 to Basadur and EP0219048 to Kud et al. published April 22,1987.

Other suitable detergents are listed in US4201824 of Voilland et al., US4240918 of Lagasse et al., US4525524 of Tung et al., US4579681, US4220918, US4787989 of Ruppert et al., EP279134A of Rhone-Poulenc Chemie, 1988, EP457205A of VBASF. DE2335044, described in 1974, all listed as references herein.

Clay Soil Removal/Anti-Redeposition Agents - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01% to about 5%.

A preferred soil removal and antiredeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are described in US Patent 4,597,898, VanderMeer, issued July 1,1986. Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds disclosed in EP 111965, Oh and Gosselink, published June 27,1984. Other clay soil removal/anti-redeposition agents that may be used include the ethoxylated amine polymers disclosed in EP111984, Gosselink, published June 27, 1984; ionic polymers; and the amine oxides disclosed in US Patent 4,548,744, Connor, issued October 22,1985. Other clay soil removal and/or antiredeposition agents known in the art may also be used in the compositions of the present invention. See US 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC) materials. These substances are known in the art.

Polymeric Dispersants - Polymeric dispersants can advantageously be used in the compositions herein at levels from about 0.1% to about 7% by weight, especially when zeolite and/or layered silicate builders are present. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. While not wishing to be bound by theory, it is believed that when polymeric dispersants are used with other builders, including low molecular weight polycarboxylates, peptization and resistance to soil release, especially through crystal growth inhibition, Redeposition improves the performance of all detergent builders.

The polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and Methylenemalonic acid. In the polymeric polycarboxylates of the present invention, the presence of monomer moieties not containing carboxylate groups such as vinyl methyl ether, styrene, ethylene, etc. is suitable provided that it does not exceed about 40% by weight .

Especially suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000. Examples of water-soluble salts of such acrylic acid polymers include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Such soluble polymers are known substances. Diehl, US3308067, issued March 7, 1967, discloses the use of such polyacrylates in detergent compositions.

Acrylic/maleic acid based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate moieties to maleate moieties in such copolymers is generally from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble acrylate/maleate copolymers are known materials and are described in EP66915, published December 15, 1982, and in EP193360, published September 3, 1986, which also describes Such polymers based on acrylates. Other useful dispersants include maleic acid/acrylic acid/vinyl alcohol terpolymers. Such materials are also described in EP193360, including for example the 45/45/10 terpolymer of acrylic acid/maleic acid/vinyl alcohol.

Another class of polymers that can be included is polyethylene glycol (PEG). PEG can exhibit dispersant properties as well as act as a clay soil removal/anti-redeposition agent. Typical molecular weights of polyethylene glycols for this use are generally from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants, such as polyaspartate, preferably have a molecular weight (average) of about 10,000.

Other polymer types more desirable for biodegradability, improved bleach stability, or laundry use include various terpolymers and hydrophobically modified copolymers, including those sold by Rohm & Haas, BASF Corp., Nippon Shokubai , and all other means for water treatment, fabric treatment or detergent applications.

Brighteners - When used in fabric laundering or treatment, any optical brightener or other brightening or brightening agent known in the art may generally be incorporated at a level of from about 0.01% to about 1.2% by weight In the detergent composition of the present invention.

Specific examples of optical brighteners useful in the compositions of the present invention are those materials described in US Patent 4,790,856, Wixon, issued December 13,1988. These brighteners include Verona's PHORWHITE range of brighteners. Other brighteners disclosed in this reference include: Ciba-Geigy's Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Arctic White CC and Artic White CWD; 2-(4-styrylphenyl)-2H-naphtho [1,2-d]triazole; 4,4'-bis(1,2,3-triazol-2-yl)stilbene; 4,4'-bis(styryl)biphenyl and aminocoumarin . Specific examples of these brighteners include: 4-methyl-7-diethylaminocoumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenylpyrazoline ; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphtho[1,2-d]oxazole and 2-(stilbene-4-yl)-2H-naphtho [1,2-d]triazole. See also US3646015, Hamilton, issued February 29,1972.

polymeric dye transfer inhibitor

The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during laundering. Typically, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases and mixture. If used, these inhibitors will generally comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2%, by weight of the composition.

The amine N-oxide polymer typically has an amine to amine N-oxide ratio of 10:1 to 1:1,000,000. However, the number of amine oxide groups in the polyamine oxide polymer can be varied by suitable copolymerization or by suitable degree of N-oxidation. Polyamine oxides of almost any degree of polymerization can be obtained. Typically, the average molecular weight is in the range of 500-1,000,000, more preferably 1,000-500,000, most preferably 5,000-100,000. This preferred material may be referred to as "PVNO", see US5633255 to Fredj.

The most preferred polyamine N-oxide for use in the detergent compositions of the present invention is poly(4-vinylpyridine-N-oxide), which has an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide It is about 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (known as "PVPVI" types) are also preferred for use in the present invention. The average molecular weight of PVPVI is preferably in the range of 5,000-1,000,000, more preferably 5,000-200,000, and most preferably 10,000-20,000. (The average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis , Vol. 113, "Modern Methods of Polymer Characterization," the disclosure of which is incorporated herein by reference.) N-ethylene of PVPVI copolymer The molar ratio of imidazole to N-vinylpyrrolidone is usually 1:1-0.2:1, more preferably 0.8:1-0.3:1, most preferably 0.6:1-0.4:1. These copolymers may be linear or branched.

Polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, can also be used in the compositions of the present invention. PVP is known to those skilled in the detergent art; see, for example, EP-A-262897 and EP-A-256696, incorporated herein by reference. Compositions comprising PVP may also comprise polyethylene glycol "PEG" having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. The ratio of PEG to PVP in ppm is preferably provided in the wash solution from about 2:1 to about 50:1, more preferably from about 3:1 to about 10:1.

The detergent compositions herein can also optionally contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners which also provide dye transfer inhibiting benefits. If used, the compositions of the present invention preferably contain from about 0.01% to 1% by weight of such optical brighteners.

Hydrophilic optical brighteners useful in the present invention include, for example, 4,4'-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino ]-2,2'-stilbene disulfonic acid and disodium salt (Tinopal-UNPA-GX), 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methyl 4,4'-bis[(4-anilino-6- Morpholino-s-triazin-2-yl)amino]2,2'-stilbene disulfonic acid sodium salt (Tinopal AMS-GX), both obtained from Ciba-Geigy Corporation.

The particular fluorescer materials selected for use in the present invention provide especially effective dye transfer inhibiting properties when used in combination with selected polymeric dye transfer inhibiting agents described herein above. This combination of selected polymers (such as PVNO and/or PVPVI) with selected optical brighteners (such as Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) is compatible with the combination of these two detergent compositions. Provides significantly better dye inhibition when used alone than in aqueous wash solutions. While not intending to be bound by any theory, it is believed that the extent to which brightener deposits onto fabrics in the wash solution can be defined by a parameter known as the "exhaustion coefficient". The exhaustion factor is generally defined as the ratio of a) the brightener species deposited on the fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are most suitable for inhibiting dye transfer in the present invention.

Other conventional optical brightener types of compounds may optionally be used in the compositions of the present invention to provide conventional fabric "brightening" benefits rather than dye transfer inhibiting benefits. Such uses are conventional and known to detergent formulators.

Chelating Agents - The detergent compositions herein may also optionally contain one or more chelating agents, especially for exotic transition metals. They are commonly found in wash water and include iron and/or manganese in water-soluble, colloidal or particulate form and may be associated with oxides or hydroxides or with soils such as humus. Preferred chelating agents are effective in controlling the transition metals, including inter alia controlling deposition of the transition metals or compounds thereof on fabrics and/or controlling undesired redox reactions in the wash medium and/or at fabric or hard surface interfaces. The chelating agents include low molecular weight as well as high molecular weight species, generally having at least one, preferably two or more donor heteroatoms, such as O or N, capable of coordinating the transition metal. Typically the chelating agent may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below.

Aminocarboxylates useful as selective chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediamine tetrakis (methylene phosphonates), such as DEQUEST. The amino phosphonates preferably do not contain alkyl or alkenyl groups of more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US3812044, Connor et al., issued May 21,1974. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), especially as described in US4704233, Hartman and Perkins, issued November 3, 1987 [S, S] isomer.

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or co-builder with, for example, insoluble builders such as zeolites, layered silicates, etc. agent.

If utilized, these chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent compositions herein. Even more preferably, if used, such chelating agents comprise from about 0.01% to about 3.0% by weight of the composition.

Suds Suppressors - Compounds for reducing or inhibiting suds formation can be incorporated into the compositions of the present invention if desired for the intended application, especially when laundering in laundry appliances. Other compositions, such as those for hand washing, would require high lather and this component can be omitted. Suds suppression is particularly important in the so-called "high strength wash method" described in US4489455 and 4489574 and in the case of European style front loading washing machines.

Various substances can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, eg, Kirk Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 7, pp. 430-447 (Wiley, 1979).

The compositions of the present invention generally contain from 0% to about 10% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and salts thereof are generally used at levels up to about 5% by weight of the detergent compositions. 0.5% to 3% by weight is preferred, although higher amounts may also be used. Preferably from about 0.01% to 1% silicone suds suppressor is used, more preferably from about 0.25% to 0.5%. In the context of the present invention, these weight percent values include any silica that may be used with the polyorganosiloxane and any suds suppressor auxiliaries that may be used. Monostearyl phosphate suds suppressors are generally used at levels of from about 0.1% to about 2% by weight of the compositions. Hydrocarbon suds suppressors are typically used at levels of from about 0.01% to about 5.0%, although higher levels can be used. Alcohol suds suppressors are generally used in amounts of 0.2% to 3% by weight of the final composition.

Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are suitable for use herein to provide additional degreasing performance. These materials are described in WO91/08281 and PCT90/01815, page 4 et seq., incorporated herein by reference. Chemically, these materials consist of polyacrylates with one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. Molecular weights can vary, but generally range from about 2,000 to about 50,000. The compositions of the present invention may contain from about 0.05% to about 10% by weight of such alkoxylated polycarboxylates.

Fabric Softeners - Various fabric softeners that go through the laundering cycle, especially the fine-grained smectite clays disclosed in US4062647, Storm and Nirschl, issued December 13, 1977, and others known in the prior art Clay can optionally be used in the compositions of the present invention at levels from about 0.5% to about 10% by weight to provide fabric softening benefits while cleaning the fabrics. Clay softeners can be used with amine and cationic softeners as disclosed in US 4,375,416, Crisp et al., issued March 1, 1983 and US 4,291,071, Harris et al. In addition, known fabric softeners, including biodegradable types, can be used in the pre-treatment, main wash, post-wash and dryer add modes in the laundry method of the present invention.

Perfumes - Perfumes and perfume components useful in the compositions and methods of the present invention include a variety of natural and synthetic chemical components including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and fragrances which can contain complex mixtures of components such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedarwood, etc. . The final perfume will generally comprise from about 0.01% to about 2% by weight of the detergent compositions herein. The individual perfume components can comprise from about 0.0001% to about 90% of the final perfume composition. Other Components - Other components useful in various detergent compositions may also be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, liquid formulations Solvents, solid fillers for block compositions. If high foam is required, a foam booster such as C ₁₀ -C ₁₆ alkanolamides may be added to the composition, generally at a content of 1%-10%. C ₁₀ -C ₁₄ monoethanols and diethanolamides are typical examples of this class of suds boosters. It is also advantageous to use such suds boosters with high sudsing co-surfactants such as the amine oxides, betaines and sultaines mentioned above. If desired, water-soluble magnesium and/or calcium salts such as magnesium chloride, magnesium sulfate, calcium chloride, calcium sulfate, etc. can also be added at a content of usually 0.1%-2% to provide additional foam and improve degreasing performance, especially for liquids Dishwashing purposes.

The various detersive components used in the compositions of the present invention can optionally be further stabilized by absorbing said components onto a porous hydrophobic substrate, which is then coated with a hydrophobic coating agent. change. The detersive component is preferably mixed with the surfactant prior to adsorption with the porous substrate. During use, the soil release component is released from the substrate into the aqueous wash solution to accomplish its intended detergency.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. For solubilizing surfactants, monohydric alcohols are preferred, but polyols, such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycol, glycerol and 1,2-propanediol). The compositions may contain from 5% to 90%, usually from 10% to 50%, of such carriers.

The detergent compositions of the present invention are preferably formulated so that when used in aqueous laundering operations, the wash water has a pH of from about 6.5 to about 11, preferably from about 7.0 to 10.5, more preferably from about 7.0 to about 9.5. Liquid dishwashing product formulations preferably have a pH of from about 6.8 to about 9.0. Laundry products are typically pH 9-11. Techniques for controlling pH within the recommended range for use include the use of buffers, bases, acids, etc., and are known to those skilled in the art.

form of composition

The compositions of the present invention can take a variety of physical forms, including granular, gel, tablet, bar and liquid forms. Compositions include so-called concentrated granular detergent compositions suitable for addition to washing machines by means of a dispensing device placed in the drum of the machine containing a load of soiled fabrics.

The average particle size of the components of the granular composition of the invention should preferably be such that no more than 5% of the particles have a diameter greater than 1.7mm and no more than 5% of the particles have a diameter smaller than 0.15mm.

The term average particle size as defined herein is calculated by sieving a sample of the composition over a set of Tyler sieves into fractions (usually 5 fractions). The resulting weight fractions are plotted against the pore size of the sieve, the average particle size being the size of the pores through which 50% by weight of the sample passes.

Certain preferred granular detergent compositions of the present invention are of the high density type currently on the market, they generally have a bulk density of at least 600 g/l, preferably 650 g/l to 1200 g/l.

Surfactant Agglomerate Particles

One of the preferred methods of incorporating surfactants into consumer products is to prepare surfactant agglomerate particles which can take the form of tablets, spheres, pellets, needles and ribbons, but are preferably in the form of granules. A preferred way of processing the granules is to agglomerate the powder with a high active surfactant slurry (eg aluminosilicate, carbonate) and to control the particle size of the resulting agglomerates within specified limits. The process involves mixing an effective amount of powder with a high active surfactant slurry in one or more agglomerators, including, for example, pan agglomerators, Z-paddle mixers or more preferably in-line Mixers, such as equipment manufactured by Schugi (Netherlands) BV, 29 Chroomstraat 8211 AS, Lelystad, The Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9 Postfach 2050 Germany. Most preferably a high shear mixer such as a Lodige CB (trade mark) is used.

Typically high active surfactant pastes are used which contain 50% to 95% by weight, preferably 70% to 85% by weight, of surfactant. The slurry can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity but low enough to avoid decomposition of the anionic surfactant used. The operating temperature of the slurry is usually in the range of 50°C to 80°C.

laundry method

The machine laundry methods of the present invention generally comprise treating soiled fabrics in a washing machine with an aqueous wash solution comprising dissolved or dispersed therein an effective amount of a machine laundry detergent composition of the present invention. An effective amount of detergent composition herein refers to 40 g to 300 g of product dissolved or dispersed in a volume of 5 to 65 liters of wash solution as typically used in conventional machine washing methods and volumes of wash solution.

As noted above, the surfactants are used in the detergent compositions of the present invention, preferably in combination with other detersive surfactants at levels effective to obtain at least one directional improvement in detergency performance. In fabric laundry compositions, the "use level" can vary widely depending not only on the type and severity of soils and stains, but also on wash water temperature, wash water volume and type of washing machine.

In a preferred aspect of use, the dispensing device is used in a washing method. The dispensing unit contains detergent product for adding product directly to the washing machine drum prior to the start of the wash cycle. Its volumetric capacity is such that it can contain sufficient detergent product as it would normally be used in a washing process.

Once the washing machine is loaded with laundry, the dispensing device with detergent product is placed in the drum. After the washing cycle of the washing machine starts, water is added to the drum, and the drum rotates periodically. The dispensing device is designed so that it holds dry detergent products but releases these products during the wash cycle with the agitation action of the rotation of the drum and due to contact with the wash water.

Furthermore, the dispensing device may be a flexible container, such as a bag or a box. The bag may be a fibrous structure coated with a water impermeable protective material to hold the contents, such as disclosed in EP0018678. Alternatively, it may be made of a water insoluble synthetic polymeric material with engineered edge seals or closures to keep out the aqueous medium as disclosed in EP0011500, 0011501, 0011502 and 0011968. A conventional form of water-loose closure contains a water-soluble adhesive placed along one side of a cassette formed of a water-impermeable polymer film, such as polyethylene or polypropylene, and sealing it.

Example

In the following examples, the abbreviations used for each component in the composition have the following meanings:

MLAS Sodium Alkylbenzene Sulfonate Destroying Crystallinity

LAS Sodium Linear Alkylbenzene Sulfonate

MBASx Medium chain branched primary alkyl (average total carbon number = x) sulfate

MBAExSz Primary mid-chain branched alkyl (average total carbon number = z) ethoxylate (average EO = x) sulfate, sodium salt

MBAEx Mid-chain branched primary alkyl (average total carbon number = x) ethoxylates (average EO = 8)

C18 1,4-disulfate 2-octadecylbutane 1,4-disulfate

Endolase Endoglucose, sold by Novo Industries A/S, activity 3000CEVU/g

MEA Monoethanolamine

DEA Diethanolamine

PG Propylene Glycol

EtOH ethanol

NaOH Sodium Hydroxide Solution

NaTS Sodium Toluene Sulfonate

Citric Acid Anhydrous Citric Acid

C _xy FA C _1X -C _1Y fatty acid

C _xy E _z C _1s-1y branched primary alcohols condensed with average z moles of ethylene oxide

Carbonate Anhydrous sodium carbonate with a particle size of 200-900 microns

Citrate Trisodium citrate dihydrate, 86.4% active, particle size distribution 425-850 microns

TFAA C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide

LMFAA C _12-14 Alkyl N-Methyl Glucamide

APA C ₈ -C ₁₀ Amidopropyl Dimethylamine

Fatty acids (C12/14) C ₁₂ -C ₁₄ fatty acids

Fatty Acids (TPK) Topped Palm Kernel Fatty Acids

Fatty Acids (RPS) Rapeseed Fatty Acids

Borax Sodium tetraborate decahydrate

PAA Polyacrylic acid (mw＝4500)

PEG Polyethylene glycol (mw=4600)

MES Alkyl Methyl Ester Sulfonate

SAS Secondary Alkyl Sulfate

NaPS Sodium Paraffin Sulfonate

Sodium C _xy AS C _1x -C _1y Alkyl Sulfate (or other salt if specified)

C _xy E _z S Sodium C _1X-1Y alkyl sulfate condensed with z moles of ethylene oxide (or other salt if specified)

C _1x-1Y branched primary alcohols condensed by C _xy E _z with average z moles of ethylene oxide

QAS R ₂ N ⁺ (CH ₃ ) _x ((C ₂ H ₄ O) _y H) _z , R ₂ =C ₈ -C ₁₈ , x+z=3, x=0-3, z=0-3, y=1-15

STPP Sodium Tripolyphosphate Anhydrous

Zeolite A Sodium aluminosilicate hydrate of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O with a primary particle size of 0.1-10 microns

NaSKS-6 crystalline _layered silicate of _the formula δ- _Na2Si2O5

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution of 400-1200 microns

Silicate Amorphous sodium silicate (SiO ₂ :Na ₂ O ratio = 2.0)

Sulfate Sodium Sulfate Anhydrous

PAE Ethoxylated tetraethylenepentamine

PIE Ethoxylated polyethyleneimine

PAEC Methylquaternized Ethoxylated Dihexamethylenetriamine

MA/AA 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000

CMC Sodium Carboxymethyl Cellulose

Protease Protease sold under the trade name Savinase by Novo Industries A/S, activity 4KNPU/g

Cellulase Cellulase sold under the tradename Carezyme by Novo Industries A/S, activity 1000 CEVU/g

Amylase Amylase sold under the tradename Termamyl 60T by Novo Industries A/S, activity 60KNU/g

Lipase Lipase sold under the tradename Lipolase by Novo Industries A/S, activity 100 kLU/g

PB1 Sodium Perborate Monohydrate Bleach

PB4 Sodium Perborate Tetrahydrate Bleach

Percarbonate Sodium percarbonate of the nominal formula 2Na ₂ CO ₃ 3H ₂ O ₂

NaDCC Sodium Dichloroisocyanurate

NOBS Nonanoyloxybenzenesulfonate, Sodium Salt

TAED Tetraacetylethylenediamine

DTPMP Diethylenetriaminepenta(methylene phosphonate), sold under the trade name Dequest 2060 by Monsanto

Photobleach Sulfonated Zinc Phthalocyanine Encapsulated with Dextrin-Soluble Polymer

Brightener 1 4,4'-bis(2-sulfostyrene)biphenyl disodium

Brightener 2 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)stilbene-2: disodium 2'-disulfonate

HEDP 1,1-Hydroxyethane diphosphonic acid

SRP1 Sulfobenzoyl end-capped ester with oxyethyleneoxy and terephthaloyl backbone

SRP2 Sulfonated Ethoxylated Terephthalate Polymer

SRP3 Methyl-terminated ethoxylated terephthalate polymer

Polysiloxane defoamer Polydimethylsiloxane foam control agent and polysiloxane-oxyalkylene copolymer as a dispersant, the foam control agent

The weight ratio to the dispersant is 10:1-100:1

lsofol 16 Condea trademark, C16 (average) Guerbet alcohol

CaCl ₂ Calcium Chloride

MgCl ₂ magnesium chloride

Diamines Alkyldiamines such as 1,3-propylenediamine, Dytek EP, Dytek A, where Dytek is a Dupont trademark,

                                                                       

DTPA Diethylenetriaminepentaacetic acid

Dimethicone SE-76 Dimethicone Gum from General Electric Silicones Division

40 (gum)/60 (fluid) weight ratio mixture of polydimethylsiloxane fluid with a viscosity of 350 centistokes

NTA Sodium Nitrilotriacetate

BPP Butoxypropoxypropanol

EGME Ethylene glycol monohexyl ether

PEG DME dimethyl polyethylene glycol, mwt2000

PVP K60 Vinylpyrrolidone homopolymer, average molecular weight 160000

Minor components Low levels of substances such as dyes, fragrances, colorants and/or filler substances (e.g. talc, sodium chloride, sulfur

salt)

Components are anhydrous unless otherwise stated.

In the following examples, all contents are expressed in % by weight of the composition. The following examples serve to illustrate the invention, but do not limit or otherwise define the scope of the invention. All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise indicated.

Example 6

Laundry detergent compositions AD suitable for hand washing soiled fabrics according to the invention were prepared as follows: A B C D. MLAS 18 twenty two 18 twenty two STPP 20 40 twenty two 28 carbonate 15 8 20 15 Silicate 15 10 15 10 protease 0 0.3 0.3 0.3 cellulase 0.5 0.3 0 0 PB1 0 10 0 10 Sodium chloride 25 15 20 10 brightener 0-0.3 0.2 0.2 0.2 Moisture and Minor Components Balance

Example 7

Laundry detergent compositions EH according to the invention suitable for hand washing soiled fabrics were prepared as follows: E. f G h MLAS twenty two 16 11 1-6 Any combination of the following substances: C45ASC45E1SC45E3SLASMBAS16.5MBAE2S15.5 0 0-5 5-15 10-20 QAS 0-5 0-1 0-5 0-3 Any combination of the following substances: C23E6.5C45E7 0-2 0-4 0-2 0-2 STPP 5-45 5-45 5-45 5-45 PAAA 0-2 0-2 0-2 0-2 CMC 0-0.5 0-0.5 0-0.5 0-0.5 protease 0.1 0-0.5 0-0.5 0-0.5 cellulase 0-0.3 0-0.3 0-0.3 0-0.3 Amylase 0-0.5 0-0.5 0-0.5 0.1 SRP1, 2 or 3 0-0.5 0.4 0-0.5 0-0.5 Brightener 1 or 2 0-0.3 0-0.2 0-0.3 0-0.2 photobleach 0-0.1 0-0.1 0.05 0-0.1 carbonate 15 10 20 15 Silicate 7 15 10 8 Sulfate 5 5 5 5 Moisture and Minor Components Balance

Example 8

A laundry detergent composition IL suitable for hand washing soiled fabrics according to the invention was prepared as follows: I J K L MLAS 18 25 15 18 QAS 0.6 0-1 0.5 0.6 Any combination of the following substances: C23E6.5C45E7 1.2 1.5 1.2 1.0 C23E3S 1.0 0 1.5 0 STPP 25 40 twenty two 25 Bleach Activator (NOBS or TAED) 1.9 1.2 0.7 0-0.8 PB1 2.3 2.4 1.5 0.7-1.7 DTPA or DTPMP 0.9 0.5 0.5 0.3 PAAA 1.0 0.8 0.5 0 CMC 0.5 1.0 0.4 0 protease 0.3 0.5 0.7 0.5 cellulase 0.1 0.1 0.05 0.08 Amylase 0.5 0 0.7 0 SRP1, 2 or 3 0.2 0.2 0.2 0 polymeric dispersant 0 0.5 0.4 0 Brightener 1 or 2 0.3 0.2 0.2 0.2 photobleach 0.005 0.005 0.002 0 carbonate 13 15 5 10 Silicate 7 5 6 7 Moisture and Minor Components Balance

Example 9

Laundry detergent compositions AE according to the invention were prepared as follows: A B C D. E. MLAS twenty two 16.5 11 15.5 10-25 Any combination of the following: C45ASC45E1SLASC16SASC14-17NaPSC14-18MESMBAS16.5MBAE2S15.5 0 1-5.5 11 16.5 0-5 QAS 0-4 0-4 0-4 0-4 0-8 C23E6.5 or C45E7 1.5 1.5 1.5 1.5 0-4 Zeolite A 27.8 27.8 27.8 27.8 20-30 PAAA 2.3 2.3 2.3 2.3 0-5 carbonate 27.3 27.3 27.3 27.3 20-30 Silicate 0.6 0.6 0.6 0.6 0-2 PB1 1.0 1.0 1.0 1.0 0-3 protease 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.5 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-1 SRP1 0.4 0.4 0.4 0.4 0-1 Brightener 1 or 2 0.2 0.2 0.2 0.2 0-0.3 PEG 1.6 1.6 1.6 1.6 0-2 Sulfate 5.5 5.5 5.5 5.5 0-6 Polysiloxane defoamer 0.42 0.42 0.42 0.42 0-0.5

Laundry detergent compositions FK according to the invention were prepared as follows: f G h I J K MLAS 32 twenty four 16 8 4 1-35 Any combination of the following: C45ASC45E1SLASC16SASC14-17NaPSC14-18MESMBAS16.5MBAE1.5S15.5 0 8 16 twenty four 28 0-35 C23E6.5 or C45E7 3.6 3.6 3.6 3.6 3.6 0-6 QAS 0-1 0-1 0-1 0-1 0-1 0-8 Zeolite A 9.0 9.0 9.0 9.0 9.0 0-20 PAA or MA/AA 7.0 7.0 7.0 7.0 7.0 0-10 carbonate 18.4 18.4 18.4 18.4 18.4 5-25 Silicate 11.3 11.3 11.3 11.3 11.3 5-25 PB1 3.9 3.9 3.9 3.9 3.9 1-6 NOBS 4.1 4.1 4.1 4.1 4.1 0-6 protease 0.9 0.9 0.9 0.9 0.9 0-1.3 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 0-0.3 SRP1 0.5 0.5 0.5 0.5 0.5 0-1 Brightener 1 or 2 0.3 0.3 0.3 0.3 0.3 0-0.5 PEG 0.2 0.2 0.2 0.2 0.2 0-0.5 Sulfate 5.1 5.1 5.1 5.1 5.1 0-10 TFAA 0-1 0-1 0-1 0-1 0-1 0-3 Polysiloxane defoamer 0.2 0.2 0.2 0.2 0.2 0-0.5 Moisture and Minor Components Balance

Example 11

A liquid laundry detergent composition LP according to the invention was prepared as follows: L m N o P MLAS 1-7 7-12 12-17 17-22 1-35 Any combination of the following: C25AExS*Na (x = 1.8-2.5) MBAE1.8S15.5MBAS15.5C25AS (linear to higher 2-alkyl) C14-17NaPSC12-16SASC18 1,4 disulfate LASC12-16MES 15-21 10-15 5-10 0-5 0-25 LMFAA 0-3.5 0-3.5 0-3.5 0-3.5 0-8 C23E9 or C23E6.5 0-2 0-2 0-2 0-2 0-8 APA 0-0.5 0-0.5 0-0.5 0-0.5 0-2 citric acid 5 5 5 5 0-8 Fatty acids (TPK or C12/14) 2-7.5 2-7.5 2-7.5 2-7.5 0-14 fatty acid (RPS) 0-3.1 0-3.1 0-3.1 0-3.1 0-3.1 EtOH 4 4 4 4 0-8 PG 6 6 6 6 0-10 MEAs 1 1 1 1 0-3 NaOH 3 3 3 3 0-7 NaTS 2.3 2.3 2.3 2.3 0-4 sodium formate 0.1 0.1 0.1 0.1 0-1 Borax 2.5 2.5 2.5 2.5 0-5 protease 0.9 0.9 0.9 0.9 0-1.3 Lipase 0.06 0.06 0.06 0.06 0-0.3 Amylase 0.15 0.15 0.15 0.15 0-0.4 cellulase 0.05 0.05 0.05 0.05 0-0.2 PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5 PIE 1.2 1.2 1.2 1.2 0-2.5 PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2 SRP2 0.2 0.2 0.2 0.2 0-0.5 Brightener 1 or 2 0.15 0.15 0.15 0.15 0-0.5 Polysiloxane defoamer 0.12 0.12 0.12 0.12 0-0.3 fumed silica 0.0015 0.0015 0.0015 0.0015 0-0.003 spices 0.3 0.3 0.3 0.3 0-0.6 dye 0.0013 0.0013 0.0013 0.0013 0-0.003 Moisture/Minor Components Balance Balance Balance Balance Balance Product pH (10%, in deionized water) 7.5-8.5 7.5-8.5 7.5-8.5 7.5-8.5 6-9.5

Example 12

A non-limiting example of making a non-aqueous liquid laundry detergent containing bleach having the following composition:

                                       

Component wt % range (wt %)

liquid phase

MLAS 15 1-35

LAS 12 0-35

C24E5 14 10-20

Hexylene glycol 27 20-30

Spices 0.4 0-1

solid

Protease 0.4 0-1

Trisodium citrate, anhydrous 4 3-6

PB1 3.5 2-7

NOBS 8 2-12

Carbonate 14 5-20

DTPA 1 0-1.5

Brightener 1 or 2 0.4 0-0.6

Foam inhibitor 0.1 0-0.3

Trace Component Balance Amount Balance Amount

The resulting composition is a stable anhydrous heavy duty liquid laundry detergent which provides outstanding stain and soil removal performance when used in normal fabric laundering operations.

Example 13

The following examples further illustrate the hand dishwashing liquids of the present invention.

S T T

Component wt % range (wt %)

MLAS 15 0.1-25

Ammonium C23AS 5 0-35

C24E1S 5 0-35

Cocoamido MEA/DEA 2.5 0-10

LMFAA 0.5 0-10

Coconut amine oxide 2.6 1-5

Betaine** 0.87/0.10 0-2/0-0.5

C9, 11E9 5 2-10

Ammonium xylenesulfonate 4 1-6

EtOH 4 0-7

Ammonium citrate 0.1 0-1

Magnesium chloride 3.3 0-4

Calcium chloride 2.5 0-4

Diamine 2 0-8

Ammonium sulfate 0.08 0-4

Hydrogen peroxide 200ppm 10-300ppm

Spices 0.18 0-0.5

Maxatase_Protease 0.50 0-1.0

Water and trace components Balance Amount Balance Amount

** Coconut Alkyl Betaine

Example 14

The following examples further illustrate the relevant shampoo formulations of the present invention:

Component U V W X Y

Ammonium C24E2S 5 3 2 10 8

Ammonium C24AS 5 5 4 5 8

MLAS 0.6 1 4 5 7

Cocamide MEA/DEA 0 0 0.68 0.68 0.8 0

PEG14000 molar weight 0.1 0.35 0.5 0.1 0

Cocamidopropyl Betaine 2.5 2.5 0 0 1.5

Cetyl Alcohol 0.42 0.42 0.42 0.5 0.5

Stearyl Alcohol 0.18 0.18 0.18 0.2 0.18

Ethylene glycol distearate 1.5 1.5 1.5 1.5 1.5

Polydimethylsiloxane 1.75 1.75 1.75 1.75 2.0

Spices 0.45 0.45 0.45 0.45 0.45

Water and trace components Balance Amount Balance Amount Balance Amount Balance Amount Balance Amount

Example 15

Various block compositions were prepared with the following compositions:

EE FF

(weight%)

MLAS 0-10 21.5

Coconut Fatty Alcohol Sulfate 0-20 0

Soda Ash 14 15

Sulfuric acid 2.5 2.5

STP 11.6 12

Calcium carbonate 39 25

Zeolite 1 0

Sodium sulfate 0 3

Magnesium Sulfate 0 1.5

Silicate 0 3.3

Talc 0 10

Coconut Fatty Alcohol 1 1

PB1 2.25 5

Protease 0 0.08

Coconut Monoethanolamide 1.2 2.0

Fluorescent agent 0.2 0.2

Substituted methylcellulose 0.5 1.4

Spices 0.35 0.35

DTPMP 0.9 0

Moisture; Trace Component Balance Amount

Example 16

Laundry detergent compositions GG-KK according to the invention were prepared as follows: GG HH II JJ KK MLAS 16.5 12.5 8.5 4 1-25 Any combination of the following: C45ASC45E1SLASC16SASC14-17NaPSC14-18MESMBAS16.5MBAE2S15.5 0-6 10 14 18.5 0-20 QAS 0-2 0-2 0-2 0-2 0-4 TFAA 1.6 1.6 1.6 1.6 0-4 C24E3, C23E6.5 or C45E7 5 5 5 5 0-6 Zeolite A 15 15 15 15 10-30 NaSKS-6 11 11 11 11 5-15 Citrate 3 3 3 3 0-8 MA/AA 4.8 4.8 4.8 4.8 0-8 HEDP 0.5 0.5 0.5 0.5 0-1 carbonate 8.5 8.5 8.5 8.5 0-15 Percarbonate or PB1 20.7 20.7 20.7 20.7 0-25 TAED 4.8 4.8 4.8 4.8 0-8 protease 0.9 0.9 0.9 0.9 0-1 Lipase 0.15 0.15 0.15 0.15 0-0.3 cellulase 0.26 0.26 0.26 0.26 0-0.5 Amylase 0.36 0.36 0.36 0.36 0-0.5 SRP1 0.2 0.2 0.2 0.2 0-0.5 Brightener 1 or 2 0.2 0.2 0.2 0.2 0-0.4 Sulfate 2.3 2.3 2.3 2.3 0-25 Polysiloxane defoamer 0.4 0.4 0.4 0-1 Moisture and Minor Components Balance

Example 17

The high density detergent formulation LL-OO of the present invention was prepared as follows: LL MM NN OO Agglomerates C45AS 11.0 4.0 0 14.0 MLAS 3.0 10.0 17.0 3.0 Zeolite A 15.0 15.0 15.0 10.0 carbonate 4.0 4.0 4.0 8.0 PAA or MA/AA 4.0 4.0 4.0 2.0 CMC 0.5 0.5 0.5 0.5 DTPMP 0.4 0.4 0.4 0.4 spray C25E5 5.0 5.0 5.0 5.0 spices 0.5 0.5 0.5 0.5 dry additives C45AS 6.0 6.0 3.0 3.0 QAS 0-20 0-20 0-20 0-20 HEDP 0.5 0.5 0.5 0.3 SKS-6 13.0 13.0 13.0 6.0 Citrate 3.0 3.0 3.0 1.0 TAED 5.0 5.0 5.0 7.0 Percarbonate 20.0 20.0 20.0 20.0 SRP1 0.3 0.3 0.3 0.3 protease 1.4 1.4 1.4 1.4 Lipase 0.4 0.4 0.4 0.4 cellulase 0.6 0.6 0.6 0.6 Amylase 0.6 0.6 0.6 0.6 Polysiloxane defoamer 5.0 5.0 5.0 5.0 Brightener 1 0.2 0.2 0.2 0.2 Brightener 2 0.2 0.2 0.2 - Balance amount (water/minor component) 100 100 100 100

Example 18

The following are examples of hard surface cleaners:

                                                                                               time 

MLAS 3.0 4.0 4.0 0.25 0.25

NaPS - 1.0 - - - -

Coconut Fatty Acid 0.5 - - - - -

C6AS Trimethylammonium - - - - - - 3.1

C24E5 - - - 2.5 - -

Carbonate 2.0 2.0 1.0 - -

Bicarbonate 2.0 - - - - -

Citrate 8.0 1.0 - 0.5 -

Sodium sulfite 0.2 - - - - -

Fatty acid (C12/14) - - - 0.4 - -

Sodium cumene sulfonate 5.0 - 2.3 -

NTA - 2.0 - - - -

Hydrogen peroxide - - - - - - - 3.0

Sulfuric acid - - - - - - - 6.0

Ammonia 1.0 - - 0.15 -

BPP 2.0 3.0 - - - -

Isopropyl Alcohol - - - - - 3.0 -

EGME - - - - - 0.75 -

Butyl Carbitol 9.5 2.0 - - - -

2-Butyl octanol - - - 0.3 - -

PEG DME - - - 0.5 - -

PVP K60 - - - 0.3 - -

Spices 2.0 0.5 - - - 0.4

Water + trace components, etc. Balance amount Balance amount Balance amount Balance amount Balance amount

Claims (7)

1. cleaning composition, it contains:

A) by the alkylaryl sulfonate surfactants system of described composition weight meter 0.1%-99.9%, it contains the alkylaryl sulfonate surfactants by the destruction degree of crystallinity of described two or more following formulas of surfactant system weight 10%-100%:

(B-Ar-D)a(M ^q+)b

Wherein D is SO ₃ ^-, M is positively charged ion or cation mixt, and q is described cationic valency, and a and b are that the numeral of selecting makes that described composition is electroneutral; Ar is selected from benzene, toluene and their combination; Contain the summation of the part of at least one uncle hydrocarbyl portion and one or more destruction degree of crystallinity that contain 5-20 carbon atom with B, the part of wherein said destruction degree of crystallinity is interrupted the described hydrocarbyl portion or the side chain of described hydrocarbyl portion; The alkylaryl sulfonate surfactants of wherein said destruction degree of crystallinity comprises at least two kinds of isomer, and it is selected from:

I) replace or during unsubstituted benzene as Ar, based on the neighbour of the link position of substituting group and Ar-,-and right-isomer; With

Ii) based on the positional isomers of the link position of substituting group and B;

Be no more than 40 ℃ degree with the degree of crystallinity destruction of wherein said alkylaryl sulfonate surfactants system to its sodium critical solubility temperature by the CST test determination; With

Also have wherein said alkylaryl sulfonate surfactants system to have at least a following character:

Biological degradation percentage ratio by improved SCAS test determination surpasses tetrapropyl benzene sulfonate; With

The weight ratio of non-season and quaternary carbon atom is at least 5: 1 in B; With

Contain alkylaryl sulfonate surfactants by the non-destruction degree of crystallinity of one or more following formulas of described surfactant system weight 0%-85%:

(L-Ar-D)a(M ^q+)b

Wherein D, M, q, a, b, Ar are as defined in the alkylaryl sulfonate surfactants that destroys degree of crystallinity; With L be the straight-chain alkyl part that contains 5-20 carbon atom;

Wherein the alkylaryl sulfonate surfactants by the described destruction degree of crystallinity of the weight at least 60% of described surfactant system is the form of isomer, and wherein Ar is connected in B on second or thricarbon atom of described straight-chain alkyl part;

B) by described composition weight meter 0.00001%-99.9% cleaning composition auxiliary component, its at least a being selected from: i) detergency enzymes; Ii) organic detergent washing assistant; Iii) oxygen bleaching agent; Iv) bleach-activating agent; V) transition metal bleach catalyzer; Vi) oxygen-transfer agent and precursor; Vii) polymerization stain remover; The water-soluble ethoxylated amine that viii) has clay soil removal and antiredeposition character; Ix) polymeric dispersant; X) polymeric dye transfer inhibitor; Xi) alkoxylate multi-carboxylate; And xii) their mixture.

2. according to the cleaning composition of claim 1, wherein Ar is a benzene.

3. according to the composition of claim 1, wherein B comprises the odd and even number carbon chain lengths.

4. according to the composition of claim 1, wherein the major portion of B is one definitely and contains the straight-chain alkyl part of 7-16 carbon atom and the part of wherein said destruction degree of crystallinity is selected from:

I) be connected in the side chain of B, it is selected from C1-C3 alkyl, C1-C3 alkoxyl group, hydroxyl and their mixture;

The part of ii) being interrupted the B structure, it is selected from ether, sulfone, siloxanes; With

Iii) their mixture.

5. according to the cleaning composition of claim 1, the degree of crystallinity destruction of wherein said alkylaryl sulfonate surfactants system to its sodium critical solubility temperature by the CST test determination is no more than 20 ℃ degree.

6. according to the cleaning composition of claim 1, the degree of crystallinity destruction of wherein said alkylaryl sulfonate surfactants system to its calcium critical solubility temperature by the CST test determination is no more than 80 ℃ degree.

7. according to the cleaning composition of claim 1, wherein the described biological degradation percentage ratio by improved SCAS test determination is at least 60%.